Preparation of sterically hindered amine ethers

ABSTRACT

A new process is described for the preparation of a compound of the formula I ##STR1## wherein R 1 , R 2 , R 3  and R 4 , independently of each other, are C 1  -C 8  alkyl or C 1  -C 5  hydroxyalkyl, or R 1  and R 2  together with the carbon atom they are attached to are C 5  -C 2  cycloalkyl, or R 3  and R 4  together with the carbon atom they are attached to are C 5  -C 12  cycloalkyl; R 5 , R 6 , R 7 , R 8  and R 9 , independently of each other, are H, C 1  -C 8  alkyl, C 2  -C 8  alkenyl, C 5  -C 12  aryl, C 1  -C 4  haloalkyl, an electron withdrawing group, or C 6  -C 12  aryl which is substituted by a residue selected from C 1  -C 4  alkyl, C 1  -C 4  alkoxy, halogen; and R 7  and R 8  together may also form a chemical bond; and R is an organic linking group containing 2-500 carbon atoms and forming, together with the carbon atoms it is directly connected to and the nitrogen atom, a substituted, 5-, 6 or 7-membered cyclic ring structure; characterized in that a compound of the formula II ##STR2## is oxidized. The compound of the formula I can be hydrogenated and/or halogenated by conventional methods. 
     Compounds of the formula I and the corresponding hydrogenated and/or halogenated compounds are well suitable as stabilizers for organic material against degradation by light, oxygen and/or heat or yellowing; some are also active as flame retardants.

The invention relates to a new process for the preparation of stericallyhindered amine ethers, new compounds of this class, their use asstabilizers for organic material against degradation by light, oxygenand/or heat and corresponding compositions.

A number of publications describe the stabilization of organic materialusing specific sterically hindered amine (HALS) compounds asstabilizers. A valuable class of sterically hindered amines arecompounds wherein the nitrogen atom is part of a heterocyclic ring andthe nitrogen atom carries an additional organic substituent linked overan oxygen atom (NOR-HALS; Kurumada et al., J. Polym. Sci, Poly. Chem.Ed. 22, 277-81 (1984); U.S. Pat No. 5,204,473); the oxygen-linkedsubstituent is introduced in these compounds by etherification of thefree oxyl- or hydroxylamine with suitable agents.

Some N-allyl nitroxides rearrange under certain conditions into amineethers (Meisenheimer rearrangement; Chem. Ber. 52, 1667 (1919); Chem.Ber. 55, 513 (1922)). Cleavage of the nitroxide with formation of alkeneand hydroxylamine (Cope elimination) is a competing reaction, the rateof which increases with increasing steric hindrance (J. March, AdvancedOrganic Chemistry, IV Ed., Wiley, 1992).

Now it has been found that, surprisingly, oxidation of a1-allyl-substituted sterically hindered amine effectively leads to thecorresponding 1-allyloxy-substituted product. The invention thereforepertains to a process for the preparation of a compound of the formula I##STR3## wherein

R₁, R₂, R₃ and R₄, independently of each other, are C₁ -C₈ alkyl or C₁-C₅ hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl; R₅, R₆, R₇, R₈and R₉, independently of each other, are H, C₁ -C₈ alkyl, C₂ -C8alkenyl,C₅ -C₁₂ aryl, C₁ -C₄ haloalkyl, an electron withdrawing group, or C₆-C₁₂ aryl which is substituted by a residue selected from C₁ -C₄ alkyl,C₁ -C₄ alkoxy, halogen; and R₇ and R₈ together may also form a chemicalbond; and R is an organic linking group containing 2-500 carbon atomsand forming, together with the carbon atoms it is directly connected toand the nitrogen atom, a substituted, 5-, 6 or 7-membered cyclic ringstructure; R preferably being a C₂ -C₅₀₀ hydrocarbon optionallycontaining 1-200 hetero atoms selected from nitrogen, oxygen,phosphorus, sulfur, silicon and halogen, and,

characterized in that a compound of the formula II ##STR4## wherein allresidues R and R₁ -R₉ are as defined for formula I, is oxidized.

R₇ and R₈ together as a chemical bond form an allenic double bond informula 1, and a triple bond in formula II.

In the compounds of formula I and II and further products, R₁, R₂, R₃and R₄ independently preferably are methyl or ethyl, especially methyl.R₅, R₆, R₇, R₈ and R₉ as an electron withdrawing group include --CN,nitro, halogen or --COOR₁₀ where R₁₀ is C₁ -C₁₂ alkyl, C₅ -C₁₂cycloalkyl, C₇ -C₉ phenylalkyl or phenyl. Preferred as electronwithdrawing group are --CN or --COOR₁₀ where R₁₀ is C₁ -C₁₂ alkyl, C₅-C₁₂ cycloalkyl or phenyl, especially wherein R₁₀ is C₁ -C₁₂ alkyl orcyclohexyl. Preferably, R₅, R₆, R₇, R₈ and R₉ independently are H ormethyl, especially H. Also preferred are compounds wherein R₅ and R₆independently are H or methyl, especially H, and R₇, R₈ and R₉independently are haloalkyl, phenyl, vinyl, nitro, CN, COOR₁₀, or R₇ andR₈ together form a chemical bond.

Further preferences for the linking group R are mainly as describedbelow for products of formulae III, IV and V.

Of special importance is a process for the preparation of a compound ofthe formula I by oxidation of a compound of the formula II, wherein R₁,R₂, R₃ and R₄, independently of each other, are C₁ -C₈ alkyl or C₁ -C₅hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl; R₅, R₆, R₇, R₈and R₉, independently of each other, are H, C₁ -C₈ alkyl, C₃ -C₈alkenyl, C₅ -C₁₂ aryl, an electron withdrawing group, C₆ -C₁₂ aryl whichis substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen; and R is a C₃-C₅₀₀ hydrocarbon optionally containing 1-200 hetero atoms selected fromnitrogen, oxygen, phosphorus, sulfur and halogen, and forming, togetherwith the two carbon and the nitrogen atom, a substituted, 6-memberedcyclic ring structure.

Aryl stands for a group obeying the Debye-Hueckel rule; preferred as C₆-C₁₂ aryl are phenyl and naphthyl.

Alkyl is a branched or unbranched radical, embracing, within thedefinitions given, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,eicosyl or docosyl.

Alkanoyl is alkyl connected over a carbonyl linkage; thus, C₂ -C₂₀alkanoyl includes acetyl, propionyl, butyryl, hexanoyl, steaoryl.

Haloalkyl is alkyl substituted by halogen, e.g. 1 or 2 halogen atoms.Halogen atoms are preferably chloro or bromo, especially bromo.

Cycloalkyl is a saturated monovalent monocyclic hydrocarbon residue,e.g. cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl;preferred is cyclohexyl.

Organic residues or hydrocarbons containing heteroatoms, such as alkylor alkylene interrupted by hetero groups like oxygen or NH, usuallycontain these heteroatoms as typical functional groups like oxo, oxa,hydroxy, carboxy, ester, amino, amido, nitro, nitrilo, isocyanato,fluoro, chloro, bromo, phosphate, phosphonate, phosphite, silyl, thio,sulfide, sulfinyl, sulfo, heterocyclyl including pyrrolyl, indyl,carbazolyl, furyl, benzofuryl, thiophenyl, benzothiophenyl, pyridyl,chinolyl, isochinolyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazolyl,benzotriazolyl, triazinyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl,and corresponding saturated and/or substituted groups like, for example,piperidyl, piperazinyl, morpholinyl etc. They may be interrupted by oneor more of these groups; usually there are no linkages of the type O--OO--N (except nitro, cyanato, isocyanato, nitroso), N--N (except inheterocyclic ring structures), N--P or P--P present, regardless of theorder.

Preferably, in organic residues or hydrocarbons containing heteroatomssuch as R there is not more than one heteroatom attached by a singlebond to the same carbon atom. A spacer consisting of one or moreheteroatoms usually is embedded in a carbon chain or ring or insertedinto a carbon-hydrogen bond.

Compounds of the formula I can be monomeric or polymeric. They contain 1or more groups of the formula I' ##STR5## In case that the compounds ofthe formula I' are polymeric, they contain a group of the formula I' inthe repeating structural unit.

Starting compounds of the formula II are known in the art or can beobtained in analogy to known compounds. Present process can start fromisolated compounds of the formula 11 or can use the solution of thesestarting compounds as obtained directly after synthesis.

In the process of present invention, the oxidation reaction can becarried out using known oxidants, e.g. oxygen, peroxides or otheroxidizing agents such as nitrates, permanganates, chlorates; preferredare peroxides, such as hydrogen peroxide based systems, especiallyperacids such as perbenzoic acid or peracetic acid. The oxidant isconveniently used in stoiciometric amount or in excess, e.g. using 1-2moles active oxyen atoms for each group of the formula I' in the desiredproduct.

The reaction can be carried out in the presence of a suitable solvent,for example an aromatic or aliphatic hydrocarbon, alcohol, ester, amide,ether, or halogenated hydrocarbon; examples are benzene, toluene,xylene, mesitylene, methanol, ethanol, propanol, butanol,dimethylformamide, dimethylsulfoxide, methylene chloride; preferred is aC₁ -C₄ alcohol, benzene, toluene, xylene, or chlorinated C₁ -C₆hydrocarbon.

Temperature and pressure are not critical and depend mainly on theoxidant system used; preferably, temperature is kept during the reactionin the range between -20° C. and +40° C. Conveniently, the pressure iskept close to atmospheric pressure, e.g. between 0.5 and 1.5 bar; whenoxidation is achieved with gaseous oxygen, the pressure of oxygen oroxygen/inertgas may exceed atmospheric pressure.

The process of present invention can be followed by further processsteps known in the art, e.g. hydrogenation of an ethylenic double bond,halogenation, e.g. bromination, of an ethylenic double bond and/orpolymerization, with or without previous isolation of the product offormula I.

Hydrogenation of the ethylenic double bond (carbon--carbon double bond)in the compound of the formula I can be achieved by methods known in theart, e.g. reaction with gaseous hydrogen under catalytic conditions orreaction with hydrogenating agents. Preferred is catalytichydrogenation; known catalysts can be employed such as Pt, Pt, Pd, Ni,Ru, Rh, on support such as carbon or without support, Raney-Ni etc.

Hydrogenation of an allenic double bond in a compound of formula Iwherein R₇ and R₈ together are a chemical bond, proceeds in 2 steps. Thefirst step leads to a partly hydrogenated product, which may be isolatedor subjected to further derivatization, and which corresponds to formulaIV ##STR6## where R, R₁ -R₆ and R₉ are as defined above.

Complete hydrogenation yields a product of the formula III ##STR7##where R, R₁ -R₆ and R₉ are as defined above for formula I and R₇ and R₈are H, C₁ -C₈ alkyl, C₃ -C₈ alkenyl, C₅ -C₁₂ aryl, C₁ -C₄ haloalkyl, anelectron withdrawing group, or C₆ -C₁₂ aryl which is substituted by aresidue selected from C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen.

Halogenation is another follow-up reaction which may be carried outsubsequent to the process of present invention, mainly according tomethods known in the art and using the appropriate reactant, e.g. assummarized in J. March, Advanced Organic Chemistry: Reaction mechanismsand Structure, 4th Edn., Wiley, 1992, p. 812. Halogen thereby is addedto the carbon--carbon double bond of a compound of formula I or IV,resulting in an α, β-dihalogenated product. The halogen reagent X₂,where X is F, Cl, Br, I or preferably Cl or Br, especially Br, can beapplied in gaseous, liquid or solid form, pure or as a solution. Halogencan also be released during the reaction in appropriate amounts using asuitable carrier substance or source.

Reactions can be carried out according to methods known in the art usinghydrogen pressures in the common range, preferably between 0.5 and about200 bar, especially between 1 and 100 bar (1 bar=10⁵ Pa). Reactions canbe carried out using suitable solbents, e.g. water, hydrocarbons likehexane, petrol fractions, toluene, xylene, esters, ethers, halogenatedhydrocarbons or alcohols like methanol or ethanol. Reactions can also becarried out without solvent. Temperatures are uncritical and are mainlyin the range between -10° C. and about 150° C., e.g. between 0° C. andthe boiling point of the solvent like the range 0-100° C. or 20-80° C.

Present invention therefore also pertains to a process for thepreparation of a compound of the formula V ##STR8## wherein R, R₁, R₂,R₃ and R₄, R₅, R₆, and R₉ are as defined for formula 1, R₇ and R₈ are H,C₁ -C₈ alkyl, C₃ -C₈ alkenyl, C₅ -C₁₂ aryl, C₁ -C₄ haloalkyl, halogen,an electron withdrawing group, or C₆ -C₁₂ aryl which is substituted by aresidue selected from C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen; and both ofR₂₀ and R₂₁ are either hydrogen or halogen; characterized in that acompound of the formula II is oxidized and the resulting intermediate offormula I is subjected to hydrogenation and/or halogenation.

The above process can also be carried out in a way wherein theintermediate of formula I is derivatized to become another structure offormula I before subjecting it to hydrogenation and/or halogenation,e.g. by esterification, dimerization, trimerization or polymerization;or wherein the intermediate of formula I is first subjected tohydrogenation, and then further derivatized, e.g. by esterification,dimerization, trimerization or polymerization.

Preferred is a process for the preparation of a compound of the formulaV wherein R is an organic linking group containing 2-500 carbon atomsand forming, together with the carbon atoms it is directly connected toand the nitrogen atom, a substituted, 5-, 6 or 7-membered cyclic ringstructure; R₁, R₂, R₃ and R₄, independently of each other, are C₁ -C₈alkyl or C₁ -C₅ hydroxyalkyl, or R₁ and R₂ together with the carbon atomthey are attached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together withthe carbon atom they are attached to are C₅ -C₁₂ cycloalkyl; R₅, R₆, andR₉, independently of each other, are H, C₁ -C₈ alkyl, C₃ -C₈ alkenyl, C₅-C₁₂ aryl, C₁ -C₄ haloalkyl, an electron withdrawing group, or C₆ -C₁₂aryl which is substituted by a residue selected from C₁ -C₄ alkyl, C₁-C₄ alkoxy, halogen; R₇ and R₈ are H, C₁ -C₈ alkyl, C₃ -C₈ alkenyl, C₅-C₁₂ aryl, C₁ -C₄ haloalkyl, halogen, an electron withdrawing group, orC₆ -C₁₂ aryl which is substituted by a residue selected from C₁ -C₄alkyl, C₁ -C₄ alkoxy, halogen; and both of R₂₀ and R₂₁ are eitherhydrogen or halogen.

Most preferred products of the process of present invention are offormulae IIIc, IVa and Va described further below.

In general, all products of present process can be used as stabilizersfor organic material against detrimental effects of light, oxygen andheat. Of special value are the compounds of formulae I, Ia, II, IV andV. Best results are achieved with compounds of formula IlIl wherein R,R₁, R₂, R₃ and R₄, are as defined for formula I and R₅, R₆, R₇, R₈ andR₉, independently of each other, are H, C₁ -C₈ alkyl, C₂ -C₈ alkenyl,C5-C₁₂ aryl, CN, COOR₁₀, where R₁₀ is as defined for formula 1, or areC₆ -C₁₂ aryl which is substituted by a residue selected from C₁ -C₄alkyl, C₁ -C₄ alkoxy. Organic material most effectively stabilized bypresent compounds is organic polymeric material described below, e.g.coatings and thermoplastic bulk polymers, films or fibers. Where thepolymers come in contact with a pesticide, e.g. a pesticide containingsulfur and/or halogen atoms, the products of present process achieveboth a stabilization against light and detrimental effects of thepesticide. This is especially important for polymers, e.g. films, tapesor fibers, used in agricultural applications, mainly polyolefines suchas PE or PP or polyolefin copolymers. Preferred compounds in thisapplication are those of formula ll, especially IIIc below.

An important utility for all products of present process is thestabilization of paper and pulp, especially paper or pulp stillcontaining lignin, against yellowing. Application of present productscan be done as described, for example, in the international patentapplication No. WO 98/04381 and the corresponding U.S. patentapplication Ser. No. 09/119567, and publications cited therein. Mostpreferred for this application is the use of a monomeric compound of theformula III, e.g. one wherein R is C₃ -C₁₂ alkylene, or C₄ -C₁₂ alkyleneinterrupted by O, NH, OCO or NHCO, R₁ -R₄ are methyl or ethyl,especially methyl, and R₅ -R₉ are each H or C₁ -C₄ alkyl, especially H;examples are 1-propyloxy-2,2,6,6-tetramethylpiperidine,1-propyloxy-2,2,6,6-tetramethylpiperidine-4-one, or the product ofpresent example 4a (see below).

Further, the products of present process can be used with advantage asflame retardants for organic polymers. Thus, by using the products ofpresent invention, an organic polymer is stabilized against detrimentaleffects of light, oxygen and heat, while the same time theinflammability of the polymer is effectively reduced. Application ofpresent products can be done as described, for example, in theinternational patent application No. WO 98113469 and the correspondingU.S. patent application Ser. No. 09/104718, and publications citedtherein, as well as EP-A-792911 or U.S. Pat. No. 5,393,812. Mostpreferred for this utility is the use of a compound of the formula IIIor V, especially those of formula IIIc below or of formula V wherein atleast one of R₅, R₆, R₇, R₈, R₉, R₂₀ or R₂₁ is halogen, especiallybromo. Present compounds can be used as flame retardants alone or incombination with known flame retardants like a flame retardant compoundselected from the halogenated, phosphorus, boron, silicon and antimonycompounds, metal hydroxides, metal hydrates and metal oxides or mixturesthereof.

It has been a further finding of this invention that some compounds offormula III are especially well suitable as stabilizers for organicmaterial against detrimental effects of light, oxygen and heat.

The invention therefore also provides compositions comprising

A) an organic polymer which is sensitive to oxidative, thermal andloractinic degradation, and

B) at least one compound of the formula IIIa, IVa or Va ##STR9## wherein

R' and R each is an organic linking group of the formula ##STR10##

E₂ is --CO-- or --(CH₂)_(p) --, where p is 0, 1 or 2; E₁ is a carbonatom carrying the two residues R₂₄ and R₂₅, or is >N--R₂₅, or is oxygen,and R₂₄ and R₂₅ are hydrogen or an organic residue, characterized inthat the linking group R in total contains 2-500 carbon atoms and forms,together with the carbon atoms it is directly connected to it and thenitrogen atom, a substituted, 5-, 6 or 7-membered cyclic ring structure;R₁, R₂, R₃ and R₄, independently of each other, are C₁ -C₈ alkyl or C₁-C₅ hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl; R₅, R₆, R₇, R₈and R₉, independently of each other, are H, C₁ -C₈ alkyl, C₂ -C₈alkenyl, C₅ -C₁₂ aryl, C₁ -C₄ haloalkyl, an electron withdrawing group,or C₆ -C₁₂ aryl which is substituted by a residue selected from C₁ -C₄alkyl, C₁ -C₄ alkoxy, halogen; R₂₀ and R₂₁ are halogen; and R₂₂ and R₂₃are hydrogen or together are a chemical bond.

Usually R' in formula IIIa is not the linking group ##STR11## whereinR₂₄ is hydrogen and R₂₅ is hydrogen or hydroxy.

Preferred is a formula IIa wherein R' is a C₇ -C₅₀₀ hydrocarboncontaining 1-200 hetero atoms selected from nitrogen, oxygen,phosphorus, sulfur and halogen, and forming, together with the twocarbon and the nitrogen atom, a substituted, 5- or 6-membered cyclicring structure, and R₁, R₂, R₃ and R₄ are as defined above.

Current invention further provides for the use of compounds of theformula IIIa for stabilizing organic polymers against oxidative, thermalor actinic degradation. The invention likewise comprises a method ofstabilizing organic polymers against thermal, oxidative and/or actinicdegradation, which comprises adding to the polymer at least one compoundof the formula IIIa.

More detailed examples of sterically hindered amines are described belowunder classes (a') to (j').

(a') A compound of the formula (1a) ##STR12## in which n₁ is a numberfrom 1 to 4, G and G₁, independently of one another, are hydrogen ormethyl, G₁₁ is n-propoxy, O--CH═C═CH₂, O--CH═CH--CH₃ or halogenatedn-propoxy, especially n-propoxy, or brominated n-propoxy;

G₁₂, if n₁ is 1, is hydrogen, C₁ -C₁₈ alkyl which is uninterrupted orinterrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl,a monovalent radical of an aliphatic, cycloaliphatic, araliphatic,unsaturated or aromatic carboxylic acid, carbamic acid orphosphorus-containing acid or a monovalent silyl radical, preferably aradical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, ofa cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or anα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms, where eachcarboxylic acid can be substituted in the aliphatic, cycloaliphatic oraromatic moiety by 1 to 3 -COOZ₁₂ groups, in which Z₁₂ is H, C₁ -C₂₀alkyl, C₃ -C₁₂ alkenyl, C₅ -C₇ cycloalkyl, phenyl or benzyl, G₁₂, if n₁is 2, is C₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, xylylene, a divalentradical of an aliphatic, cycloaliphatic, araliphatic or aromaticdicarboxylic acid, dicarbamic acid or phosphorus-containing acid or adivalent silyl radical, preferably a radical of an aliphaticdicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic oraromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic,cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms,where each dicarboxylic acid may be substituted in the aliphatic,cycloaliphatic or aromatic moiety by one or two --COOZ₁₂ groups, G₁₂, ifn₁ is 3, is a trivalent radical of an aliphatic, cycloaliphatic oraromatic tricarboxylic acid, which may be substituted in the aliphatic,cycloaliphatic or aromatic moiety by --COOZ₁₂, of an aromatictricarbamic acid or of a phosphorus-containing acid, or is a trivalentsilyl radical, and G₁₂, if n₁ is 4, is a tetravalent radical of analiphatic, cycloaliphatic or aromatic tetracarboxylic acid.

The carboxylic acid radicals mentioned above are in each case taken tomean radicals of the formula (--CO)_(x) R, where x is as defined above,and the meaning of R arises from the definition given.

Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-hexadecyl or n-octadecyl.

Examples of several G₁₂ radicals are given below.

If G₁₂ is a monovalent radical of a carboxylic acid, it is, for example,an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

If G₁₂ is a monovalent silyl radical, it is, for example, a radical ofthe formula --(C_(j) H_(2j))--Si(Z')₂ Z", in which j is an integer inthe range from 2 to 5, and Z' and Z", independently of one another, areC₁ -C₄ alkyl or C₁ -C₄ alkoxy.

If G₁₂ is a divalent radical of a dicarboxylic acid, it is, for example,a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl,itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl,butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl orbicycloheptenedicarbonyl radical or a group of the formula ##STR13##

If G₁₂ is a trivalent radical of a tricarboxylic acid, it is, forexample, a trimellitoyl, citryl or nitrilotriacetyl radical.

If G₁₂ is a tetravalent radical of a tetracarboxylic acid, it is, forexample, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acidor of pyromellitic acid.

If G₁₂ is a divalent radical of a dicarbamic acid, it is, for example,hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

Preference is given to compounds of the formula (1a) in which G and G₁are hydrogen, G₁₁ is hydrogen or methyl, n₁ is 2 and G₁₂ is the diacylradical of an aliphatic dicarboxylic acid having 4-12 carbon atoms.

(b') A compound of the formula (1b) ##STR14## in which G and G₁,independently of one another, are hydrogen or methyl, G₁₁ is n-propoxy,G₁₃ is hydrogen, C₁ -C₁₂ alkyl, C₂ -C₅ hydroxyalkyl, C₅ -C₇ cycloalkyl,C₇ -C₈ aralkyl, C₁ -C₁₈ alkanoyl, C₃ -C₅ alkenoyl, benzoyl or a group ofthe formula (1b-1) ##STR15## n₂ is the number 1, 2 or 3; and G₁₄, if n₂is 1, is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₅ -C₇ cycloalkyl, C₁-C₄ alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl orcarbamide group, glycidyl, a group of the formula --CH₂ -CH(OH)--Z or ofthe formula --CONH--Z, in which Z is hydrogen, methyl or phenyl;

G₁₄, if n₂ is 2, is C₂ -C₁₂ alkylene, C₆ -C₁₂ arylene, xylylene, a --CH₂-CH(OH)--CH₂ group or a --CH₂ -CH(OH)--CH₂ --O--D--O-- group, in which Dis C₂ -C₁₀ alkylene, C₆ -C₁₅ arylene, C₆ -C₁₂ cycloalkylene, or,provided that G₁₃ is not alkanoyl, alkenoyl or benzoyl, G₁₄ canalternatively be 1-oxo-C₂ -C₁₂ alkylene, a divalent radical of analiphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamicacid or alternatively the group --CO--, G₁₄, if n₂ is 3, is a group##STR16## or, if n₂ is 1, G₁₃ and G₁₄ together can be the divalentradical of an aliphatic, cycloaliphatic or aromatic 1,2- or1,3-dicarboxylic acid.

Some examples for the radicals G₁₃, G₁₄ and D are given below.

Any alkyl substituents are as defined above for (a').

Any C₅ -C₇ cycloalkyl substituents are, in particular, cyclohexyl.

C₇ -C₈ aralkyl G₁₃ is, in particular, phenylethyl or especially benzyl.

C₂ -C₅ hydroxyalkyl G₁₃ is, in particular, 2-hydroxyethyl or2-hydroxypropyl.

C₁ -C₁₈ alkanoyl G₁₃ is, for example, formyl, acetyl, propionyl,butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, butpreferably acetyl, and C₃ -C₅ alkenoyl G₁₃ is, in particular, acryloyl.

C₂ -C₈ alkenyl G₁₄ is, for example, allyl, methallyl, 2-butenyl,2-pentenyl, 2-hexenyl or 2-octenyl.

G₁₄ as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted C₁-C₄ alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl,2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl,2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

Any C₂ -C₁₂ alkylene radicals are, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene. Any C₆ -C₁₅ arylene substituents are,for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C₆ -C₁₂ cycloalkylene is, in particular, cyclohexylene.

G₁₄ as 1--oxo--C₂ -₁₂ alkylene is preferably a group ##STR17##

Preference is given to compounds of the formula (1b) in which n₂ is 1 or2, G and G₁ are hydrogen, G₁₃ is hydrogen, C₁ -C₁₂ alkyl or a group ofthe formula ##STR18## and G₁₄, in the case where n₂ =1, is hydrogen orC₁ -C₁₂ alkyl, and, in the case where n₂ =2, is C₂ -C₈ alkylene or1-oxo-C₂ -C₈ alkylene.

(c') A compound of the formula (1c) ##STR19## in which n₃ is the number1 or 2, G, G₁ and G₁₁ are as defined under (b'), and G₁₅, if n₃ is 1, isC₂ -C₈ alkylene, C₂ -C₈ hydroxyalkylene or C₄ -C₂₂ acyloxyalkylene, andif n₃ is 2, G₁₅ is the (--CH₂)₂ C(CH₂ --)₂ group.

C₂ -C₈ alkylene or C₂ -C₈ hydroxyalkylene G₁₅ is, for example, ethylene,1-methylethylene, propylene, 2-ethylpropylene or2-ethyl-2-hydroxymethylpropylene.

C₄ -C₂₂ acyloxyalkylene G₁₅ is, for example,2-ethyl-2-acetoxymethylpropylene.

(d') A compound of the formula (1d-1), (1 d-2) or (1 d-3), ##STR20## inwhich n₄ is the number 1 or 2, G, G₁ and G₁₁ are as defined under (b'),G₁₆ is hydrogen, C₁ -C₁₂ alkyl, allyl, benzyl, glycidyl or C₂ -C₆alkoxyalkyl, and G₁₇, if n₄ is 1, is hydrogen, C₁ -C₁₂ alkyl, C₃ -C₅alkenyl, C₇ -C₉ aralkyl, C₅ -C₇ cycloalkyl, C₂ -C₄ hydroxyalkyl, C₂ -C₆alkoxyalkyl, C₆ -C₁₀ aryl, glycidyl or a group of the formula--(CH₂)_(p) --COO--Q or --(CH₂)_(p) --O--CO--Q, in which p is 1 or 2,and Q is C₁ -C₄ alkyl or phenyl, and G₁₇, if n is 2, is C₂ -C₁₂alkylene, C₄ -C₁₂ alkenylene, C₆ -C₁₂ arylene, a group of the formula--CH₂ -CH(OH)--CH₂ --O--D'--O--CH₂ --CH(OH)--CH₂ --, in which D' is C₂-C₁₀ alkylene, C₆ -C₁₅ arylene, C₆ -C₁₂ cycloalkylene or a group of theformula --CH₂ CH(OD")CH₂ --(OCH₂ -CH(OD")CH₂)₂ --, in which D" ishydrogen, C₁ -C₁₈ alkyl, allyl, benzyl, C₂ -C₁₂ alkanoyl or benzoyl, T₁and T₂, independently of one another, are hydrogen, C₁ -C₁₈ alkyl orunsubstituted or halogen- or C₁ -C₄ alkyl-substituted C₆ -C₁₀ aryl or C₇-C₉ aralkyl, or T₁ and T₂ together with the carbon atom bonding themform a C₅ -C₁₄ cycloalkane ring.

A compound of the formula (1d-3) is preferred.

Some examples of the several variables in the formulae (1d-1), (1 d-2)and (1 d-3) are given below.

Any C₁ -C₁₂ alkyl substituents are, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any C₁ -C₁₈ alkyl substituents can be, for example, the abovementionedgroups and in addition, for example, n-tridecyl, n-tetradecyl,n-hexadecyl or n-octadecyl.

Any C₂ -C₆ alkoxyalkyl substituents are, for example, methoxymethyl,ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl,ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl orpropoxypropyl.

C₃ -C₅ alkenyl G₁₇ is, for example, 1-propenyl, allyl, methallyl,2-butenyl or 2-pentenyl.

C₇ -C₉ aralkyl G₁₇, T₁ and T₂ are, in particular, phenethyl orespecially benzyl. If T₁ and T₂ together with the carbon atom form acycloalkane ring, this can be, for example, a cyclopentane, cyclohexane,cyclooctane or cyclododecane ring.

C₂ -C₄ hydroxyalkyl G₁₇ is, for example, 2-hydroxyethyl,2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C₆ -C₁₀ aryl G₁₇, T₁ and T₂ are, in particular, phenyl or α- orβ-naphthyl, which are unsubstituted or substituted by halogen or C₁ -C₄alkyl.

C₂ -C₁₂ alkylene G₁₇ is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

C₄ -C₁₂ alkenylene G₁₇ is, in particular, 2-butenylene, 2-pentenylene or3-hexenylene.

C₆ -C₁₂ arylene G₁₇ is, for example, o-, m- or p-phenylene,1,4-naphthylene or 4,4'-diphenylene.

C₂ -C₁₂ alkanoyl D" is, for example, propionyl, butyryl, octanoyl,dodecanoyl, but preferably acetyl.

C₂ -C₁₀ alkylene, C₆ -C₁₅ arylene or C₆ -C₁₂ cycloalkylene D' have, forexample, one of the definitions given for D under (b').

(e') A compound of the formula (1e) ##STR21## in which n₅ is the number1 or 2, and G₁₈ is a group of the formula ##STR22## in which G and G₁₁are as defined under (b'), and G₁ and G₂ are hydrogen, methyl or,together, are a substituent ═O,

E is --O -- or --ND'"--,

A is C₂ -C₆ alkylene or --(CH₂)₃ --O-- and

x₁ is the number 0 or 1,

D'" is hydrogen, C₁ -C₁₂ alkyl, C₂ -C₅ hydroxyalkyl or C₅ -C₇cycloalkyl,

G₁₉ is identical to G₁₈ or is one of the groups --N(G₂₁)(G₂₂), --OG₂₃,--N(H)(CH₂ OG₂₃) or --N(CH₂ OG₂₃)₂,

G₂₀, if n=1, is identical to G₁₈ or G₁₉ and, if n=2, is an --E--D^(IV)--E-- group, in which D^(IV) is C₂ -C₈ alkylene or C₂ -C₈ alkylene whichis interrupted by 1 or 2-NG₂₁ - groups,

G₂₁ is C₁ -C₁₂ alkyl, cyclohexyl, benzyl or C₁ -C₄ -hydroxyalkyl or agroup of the formula ##STR23## G₂₂ is C₁ -C₁₂ alkyl, cyclohexyl, benzylor C₁ -C₄ hydroxyalkyl, and G₂₃ is hydrogen, C₁ -C₁₂ alkyl or phenyl, orG₂₁ and G₂₂ together are C₄ -C₅ alkylene or C₄ -C₅ oxaalkylene, forexample --CH₂ CH₂ --O--CH₂ CH₂ --, or a group of the formula --CH₂ CH₂--N(G₁₁)--CH₂ CH₂ --.

Some examples of the several variables in the formula (1e) are givenbelow.

Any C₁ -C₁₂ alkyl substituents are, for example, methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Any C₅ -C₇ cycloalkyl substituents are, for example, cyclopentyl,cyclohexyl or cycloheptyl. Cyclohexyl is preferred.

C₂ -C₆ alkylene A is, for example, ethylene, propylene,2,2-dimethylpropylene, tetramethylene or hexamethylene.

If G₂₁ and G₂₂ together are C₄ -C₅ alkylene or oxaalkylene, they are,for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds from this class are thecompounds of the following formulae: ##STR24##

(f') A compound of the formula (1f) ##STR25## wherein G₁₁ is as definedunder (b').

(g') Oligomeric or polymeric compounds whose recurring structural unitcontains a 2,2,6,6-tetraalkylpiperidinyl radical, in particularpolyesters, polyethers, polyamides, polyamines, polyurethanes,polyureas, polyaminotriazines, poly(meth)acrylates,poly(meth)acrylamides and copolymers thereof which contain suchradicals.

Examples of 2,2,6,6-polyalkylpiperidine compounds from this class arethe compounds of the following formulae, where m₁ to m₁₄ is a numberfrom 2 to about 200, preferably 2 to 100, for example 2 to 50, 2 to 40or 3 to 40 or 4 to 10.

The meanings of the end groups which saturate the free valences in theoligomeric or polymeric compounds listed below depend on the processesused for the preparation of said compounds. The end groups can also inaddition be modified after the synthesis of the compounds.

Examples are compounds of the formula (1g-1) ##STR26## in which theindex n ranges from 1 to 15, being especially from the range 3-9; R₁₂ isC₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, C₅ -C₇ cycloalkylene, C₅ -C₇cycloalkylenedi(C₁ -C₄ alkylene), C₁ -C₄ alkylenedi(C₅ -C₇cycloalkylene), phenylenedi(C₁ -C₄ alkylene) or C₄ -C₁₂ alkyleneinterrupted by 1,4-piperazinediyl, --O-- or >N--X₁ with X₁ being C₁ -C₁₂acyl or (C₁ -C₁₂ alkoxy)carbonyl or having one of the definitions of R₁₄given below except hydrogen; or R₁₂ is a group of the formula (Ib') or(Ic'); ##STR27## with m being 2 or 3, X₂ being C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄alkyl; phenyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄alkyl or C₁ -C₄ alkoxy; C₇ -C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁ -C₄ alkyl; and the radicals X₃being independently of one another C₂ -C₁₂ alkylene; the radicals B areindependently of one another Cl, --OR₁₃, --N(R₁₄)(R₁₅) or a group of theformula (IIId); ##STR28## R₁₃, R₁₄ and R₁₅, which are identical ordifferent, are hydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which isunsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkyl; C₃ -C₁₈ alkenyl,phenyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkylor C₁ -C₄ alkoxy; C₇ -C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁ -C₄ alkyl; tetrahydrofurfurylor C₂ -C₄ alkyl which is substituted in the 2, 3 or 4 position by --OH,C₁ -C₈ alkoxy, di(C₁ -C₄ alkyl)amino or a group of the formula (Ie');##STR29## with Y being --O--, --CH₂ --, --CH₂ CH₂ -- or >N--CH₃, or--N(R₁₄)(R₁₅) is additionally a group of the formula (Ie'); X is --O--or >N--R₁₆ ; R₁₆ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₈ alkenyl, C₅ -C₁₂cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄alkyl; C₇ -C₉ phenylalkyl which is unsubstituted or substituted on thephenyl by 1, 2 or 3 C₁ -C₄ alkyl; tetrahydrofurfuryl, a group of theformula (IIIf), ##STR30## or C₂ -C₄ alkyl which is substituted in the 2,3 or 4 position by --OH, C₁ -C₈ alkoxy, di(C₁ -C₄ alkyl)amino or a groupof the formula (Ie'); R₁₁ has one of the definitions given for R₁₆.

In these compounds, the end group bonded to the triazine residue can be,for example, a group B or --N(R₁₁)--R₁₂ --B, such as chlorine or a group##STR31## and the end group bonded to the diamino group can be, forexample, hydrogen or a di-B-substituted triazinyl group, such as a group##STR32##

It may be convenient to replace the chlorine attached to the triazine bye.g. --OH or an amino group. Suitable amino groups are typically:pyrrolidin-1-yl, morpholino, --NH₂, --N(C₁ -C₈ alkyl)₂ and --NY'(C₁ -C₈alkyl) wherein Y' is hydrogen or a group of the formula ##STR33##

In the above shown oligomeric and polymeric compounds, examples of alkylare methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,eicosyl and docosyl; examples of cycloalkyl are cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl; an example of C₇ -C₉ phenylalkyl is benzyl;and examples of alkylene are ethylene, propylene, trimethylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene,trimethylhexamethylene, octamethylene and decamethylene.

(h') A compound of the formula (1h) ##STR34## in which n₆ is the number1 or 2, G and G₁₁, are as defined under (a'), and G₁₄ is as definedunder (b').

(i') A compound of the formula (1i) ##STR35## wherein the radicals G₃₉,independently of one another, are a group of the formula (1i-1)##STR36## in which G₄₀ is C₁ -C₁₂ alkyl or C₂ -C₁₂ cycloalkyl, G₄₁ is C₂-C₁₂ alkylene and G₄₂ is hydrogen, C₁ -C₈ alkyl, --O, --CH₂ CN, C₃ -C₆alkenyl, C₇ -C₉ phenylalkyl, C₇ -C₉ phenylalkyl which is substituted onthe phenyl radical by C₁ -C₄ alkyl; or C₁ -C₈ acyl.

Alkyl is for example C₁ -C₄ alkyl, in particular methyl, ethyl, propylor butyl.

Cycloalkyl is preferably cyclohexyl.

Alkylene is for example ethylene, propylene, trimethylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene orhexamethylene.

Alkenyl is preferably allyl.

Phenylalkyl is preferably benzyl.

Acyl is preferably acetyl.

Especially preferred is a compound of the formula IIIb ##STR37## inwhich

the radicals A are independently of one another --OR₁₃, --N(R₁₄)(R₁₅) ora group of the formula (IIId); ##STR38##

X is --O-- or >N--R₁₆ ;

R₁₆ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₈ alkenyl, C₅ -C₁₂ cycloalkylwhich is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkyl; C₇ -C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2or 3 C₁ -C₄ alkyl; tetrahydrofurfuryl, a group of the formula (IIIf),##STR39## or C₂ -C₄ alkyl which is substituted in the 2, 3 or 4 positionby --OH, C₁ -C₈ alkoxy, di(C₁ -C₄ alkyl)amino or a group of the formula(Ie'); R₁₁ has one of the definitions given for R₁₆ ; and the radicals Bhave independently of one another one of the definitions given for A;and where formula (Ie') and all other symbols are as defined above forformula Ia.

The radicals B, R₁₁ and R₁₂ in the individual recurrent units may beidentical or different within the meanings given.

(j') A compound of the formula (2a) ##STR40## in which

R₁, R₂, R₃ and R₄, independently of each other, are C₁ -C₈ alkyl or C₁-C₅ hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl.

Specific examples for hydrogenated products of present invention includethe following compounds:

1-propoxy-2,2,6,6-tetramethyl-4-piperidone,1-propoxy-2,2,6,6-tetramethyl-4-piperidol,bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)-(3',5'-di-tert.butyl-4'-hydroxybenzyl)butylmalonate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)succinate,N,N'-bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexane-1,6-diamine,N-butyl-1-propoxy-2,2,6,6-tetramethyl-4-piperidinamine,5-(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)-2-cyclo-undecyloxazole,1,6-hexanediyl-N,N'-bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl-formamide),1,5-dioxaspiro(5,5)undecane-3,3-dicarboxylic acidbis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) ester,1,5,8,12-tetrakis(2',4'-bis(1"-propoxy-2",2",6",6"-tetramethyl-4"-piperidyl(butyl)amino)-1',3',5'-triazin-6'-yl)-1,5,8,12-tetraazadodecane,1,3,5-tris(N-cyclohexyl-N-(1-propoxy-2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine,linear or cyclic condensates ofN,N'-bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamineand 4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis-(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1'-(1,2-ethanediyl)-bis-(4-propoxy-3,3,5,5-tetramethylpiperazinone),4-benzoyl-1-propoxy-2,2,6,6-tetramethylpiperidine,4-stearyloxy-1-propoxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-8-propoxy-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decan-2,4-dione,linear or cyclic condensates ofN,N'-bis-(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamineand 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-propoxy-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione,3-dodecyl-1-(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,a mixture of 4-hexadecyloxy- and4-stearyloxy-1-propoxy-2,2,6,6-tetramethylpiperidine, a condensationproduct ofN,N'-bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamineand 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensationproduct of 1,2-bis(3-aminopropylamino)ethane and2,4,6-trichloro-1,3,5-triazine as well as4-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidine;N-(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-8-propoxy-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,a reaction product of8-propoxy-7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin,N,N'-bis-formyl-N,N'-bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,poly[methyl-propyl-3-oxy-4-(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with1-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine; or the compound

    R--NH--(CH.sub.2).sub.3 --N(R)--(CH.sub.2).sub.2 --N(R)--(CH.sub.2).sub.3 --NH--R, with R═ ##STR41##

Compounds of the formulae I, III and V, especially IIIa and IIIb can beemployed with advantage for stabilizing organic material against thedamaging effect of light, oxygen and/or heat, especially for stabilizingsynthetic organic polymers or compositions containing them. They arenotable for high thermal stability, substrate compatibility and goodpersistence in the substrate.

Examples of polymers which can be stabilized in this way are thefollowing:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/ styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

Of particular interest is the use of compounds of the formula IIIa asstabilizers in synthetic organic polymers, for example a coating or abulk polymer or article formed therefrom, especially in thermoplasticpolymers and corresponding compositions as well as in coatingcompositions. Thermoplastic polymers of most importance in presentcompositions are polyolefines and their copolymers, such as listed aboveunder items 1-3, thermoplastic polyolefin (TPO), thermoplasticpolyurethan (TPU), thermoplastic rubber (TPR), polycarbonate, such as initem 19 above, and blends, such as in item 28 above. Of utmostimportance are polyethylene (PE), polypropylene (PP), polycarbonate (PC)and polycarbonate blends such as PC/ABS blends, as well as in acid ormetal catalyzed coating compositions.

In general the compounds of present invention are added to the materialto be stabilized in amounts of from 0.1 to 10%, preferably from 0.01 to5%, in particular from 0.01 to 2% (based on the material to bestabilized). Particular preference is given to the use of the novelcompounds in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.Where compounds of present invention are used as flame retardants,dosages are usually higher, e.g. 0.1 to 25% by weight, mainly 0.1 to 10%by weight of the organic material to be stabilized and protected againstinflammation.

Incorporation into the materials can be effected, for example, by mixingin or applying the compounds of the formula I, IIIa, IV, V and, ifdesired, further additives by the methods which are customary in theart. Where polymers are involved, especially synthetic polymers,incorporation can take place prior to or during the shaping operation,or by applying the dissolved or dispersed compound to the polymer, withor without subsequent evaporation of the solvent. In the case ofelastomers, these can also be stabilized as latices. A furtherpossibility for incorporating the compounds of the formula IIIa intopolymers is to add them before, during or directly after thepolymerization of the corresponding monomers or prior to crosslinking.In this context the compound of the formula IIIa can be added as it isor else in encapsulated form (for example in waxes, oils or polymers).In the case of addition prior to or during the polymerization, thecompounds of the formula IIIa can also act as a regulator of the chainlength of the polymers (chain terminator).

The compounds of the formula IIIa can also be added in the form of amasterbatch containing said compound in a concentration, for example, offrom 2.5 to 25% by weight to the polymers that are to be stabilized.

The compounds of the formula IIIa can judiciously be incorporated by thefollowing methods:

as emulsion or dispersion (e.g. to latices or emulsion polymers),

as a dry mixture during the mixing in of additional components orpolymer mixtures,

by direct introduction into the processing apparatus (e.g. extruders,internal mixers, etc),

as solution or melt.

Novel polymer compositions can be employed in various forms and/orprocessed to give various products, for example as (to give) films,fibres, tapes, moulding compositions, profiles, or as binders forcoating materials, adhesives or putties.

In addition to the compounds of the formula IIIa the novel compositionsmay as additional component C comprise one or more conventionaladditives such as, for example, those indicated below.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,2,4-di-methyl-6-(1'-methylheptadec-1'-yl)phenol,2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,6-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol),4,4'-thiobis(6-tert-butyl-2-methylphenol),4,4'-thiobis-(3,6-di-sec-amylphenol),4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol),2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2'-methylenebis(4-methyl-6-cyclohexylphenol),2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(4,6-di-tert-butyl-phenol),2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4'-methylenebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O--, N-- and S-benzyl compounds, for example3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol. p 1.10. TriazineCompounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or poly-hydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β(3-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazide,N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N'-di-isopropyl-p-phenylenediamine,N,N'-di-secbutyl-p-phenylenediamine,N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N'-bis(1-methylheptyl)-p-phenylenediamine,N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine,N,N'-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N'-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,N-cyclohexyl-N'-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,tertoctylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers

2.1. 2-(2'-Hydroxylphenyl)benzotriazoles, for example2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2'-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R--CH₂ CH₂ --COO--CH₂ CH₂ .brketclose-st.₂ whereR=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

2.2.2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxyand 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tertbutylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tertbutylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensateof2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxymethylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butyl-amino]-6-(2-hydroxyethyl)amino-1,3,5-triazine.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide,N,N'-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-{2-hydroxy-4-[1-octyloxycarbonyl-ethoxy]phenyl}-4,6-bis(4-phenylphenyl)-1,3,5-triazinewherein the octyl moiety is a mixture of different isomers.

3. Metal deactivators, for example N,N'-diphenyloxamide,N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyldihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite],2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite.

Especially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafose®, Ciba-Geigy),tris(nonylphenyl) phosphite, ##STR42##

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhy-droxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zinkpyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers).

12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The conventional additives are judiciously employed in amounts of0.1-10% by weight, for example 0.2-5% by weight, based on the materialto be stabilized.

Costabilizers optionally to be added to the stabilizer mixture of theinvention are preferably further light stabilizers, for instance thoseof the 2-hydroxyphenyl-benztriazole, 2-hydroxyphenyl-triazine,benzophenone or oxalanilide classes, e.g. as described in EP-A-453396,EP-A-434608, U.S. Pat. No. 5,298,067, WO 94/18278, GB-A-2297091 and WO96/28431, and/or further hindered amines derived from2,2,6,6-tetraalkylpiperidine containing at least one group of theformula ##STR43## in which G is hydrogen or methyl, especially hydrogen;examples of tetraalkylpiperidine derivatives which can be used ascostabilizers with mixtures of the invention are given in EP-A-356 677,pages 3-17, sections a) to f). These sections of this EP-A are regardedas part of the present description.

Likewise of particular interest is the use of the novel mixturescomprising compounds of the formula IIIa as stabilizers for coatings,for example for paints. The invention therefore also relates to thosecompositions whose component (A) is a film-forming binder for coatings.

The novel coating composition preferably comprises 0.01-10 parts byweight of (B), in particular 0.05-10 parts by weight of (B), especially0.1-5 parts by weight of (B), per 100 parts by weight of solid binder(A).

Multilayer systems are possible here as well, where the concentration ofthe novel stabilizer (component (B)) in the outer layer can berelatively high, for example from 1 to 15 parts by weight of (B), inparticular 3-10 parts by weight of (B), per 100 parts by weight of solidbinder (A).

The use of the novel stabilizer in coatings is accompanied by theadditional advantage that it prevents delamination, i.e. the flaking-offof the coating from the substrate. This advantage is particularlyimportant in the case of metallic substrates, including multilayersystems on metallic substrates.

The binder (component (A)) can in principle be any binder which iscustomary in industry, for example those described in Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.368-426, VCH, Weinheim 1991. In general, it is a film-forming binderbased on a thermoplastic or thermosetting resin, predominantly on athermosetting resin. Examples thereof are alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) can be a cold-curable or hot-curable binder; the additionof a curing catalyst may be advantageous. Suitable catalysts whichaccelerate curing of the binder are described, for example, in Ullmann'sEncyclopedia of Industrial Chemistry, Vol. Al 8, p.469, VCHVerlagsgesellschaft, Weinheim 1991.

Preference is given to coating compositions in which component (A) is abinder comprising a functional acrylate resin and a crosslinking agent.

Examples of coating compositions containing specific binders are:

1. paints based on cold- or hot-crosslinkable alkyd, acrylate,polyester, epoxy or melamine resins or mixtures of such resins, ifdesired with addition of a curing catalyst;

2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates;

3. one-component polyurethane paints based on blocked isocyanates,isocyanurates or polyisocyanates which are deblocked during baking, ifdesired with addition of a melamine resin;

4. one-component polyurethane paints based on aTrisalkoxycarbonyltriazine crosslinker and a hydroxyl group containingresin such as acrylate, polyester or polyether resins;

5. one-component polyurethane paints based on aliphatic or aromaticurethaneacrylates or polyurethaneacrylates having free amino groupswithin the urethane strukture and melamine resins or polyether resins,if necessary with curing catalyst;

6. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates;

7. two-component paints based on (poly)ketimines and an unsaturatedacrylate resin or a polyacetoacetate resin or a methacrylamidoglycolatemethyl ester;

8. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides;

9. two-component paints based on acrylate resins containing anhydridegroups and on a polyhydroxy or polyamino component;

10. two-component paints based on acrylate-containing anhydrides andpolyepoxides;

11. two-component paints based on (poly)oxazolines and acrylate resinscontaining anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

12. two-component paints based on unsaturated polyacrylates andpolymalonates;

13. thermoplastic polyacrylate paints based on thermoplastic acrylateresins or externally crosslinking acrylate resins in combination withetherified melamine resins;

14. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins.

In addition to components (A) and (B), the coating composition accordingto the invention preferably comprises as component (C) a lightstabilizer of the sterically hindered amine type, the2-(2-hydroxyphenyl)-1,3,5-triazine and/or2-hydroxyphenyl-2H-benzotriazole type, for example as mentioned in theabove list in sections 2.1, 2.6 and 2.8. Further examples for lightstabilizers of the 2-(2-hydroxyphenyl)-1,3,5-triazine typeadvantageously to be added can be found e.g. in the publications U.S.Pat. No. 4,619,956, EP-A-434608, U.S. Pat. No. 5,198,498, U.S. Pat. No.5,322,868, U.S. Pat. No. 5,369,140, U.S. Pat. No. 5,298,067,WO-94/18278, EP-A-704437, GB-A-2297091, WO-96/28431. Of specialtechnical interest is the addition of the2-(2-hydroxyphenyl)-1,3,5-triazines and/or2-hydroxyphenyl-2H-benzotriazoles, especially the2-(2-hydroxyphenyl)-1,3,5-triazines.

Component (C) is preferably used in an amount of 0.05-5 parts by weightper 100 parts by weight of the solid binder.

Apart from components (A), (B) and, if used, (C), the coatingcomposition can also comprise further components, examples beingsolvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents,drying catalysts and/or levelling agents. Examples of possiblecomponents are those described in Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim 1991.

Possible drying catalysts or curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metals Al, Ti or Zr, or organometalliccompounds such as organotin compounds, for example.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, theoctoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates.

Examples of metal chelates are the aluminium, titanium or zirconiumchelates of acetylacetone, ethyl acetylacetate, salicylaldehyde,salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate,and the alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctoate.

Examples of amines are, in particular, tertiary amines, for exampletributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and salts thereof. Furtherexamples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride.

Amino-containing resins are simultaneously binder and curing catalyst.Examples thereof are amino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

The novel coating compositions can also be radiation-curable coatingcompositions. In this case, the binder essentially comprises monomericor oligomeric compounds containing ethylenically unsaturated bonds,which after application are cured by actinic radiation, i.e. convertedinto a crosslinked, high molecular weight form. Where the system isUV-curing, it generally contains a photoinitiator as well. Correspondingsystems are described in the abovementioned publication Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pages451-453. In radiation-curable coating compositions, the novelstabilizers can also be employed without the addition of stericallyhindered amines.

The coating compositions according to the invention can be applied toany desired substrates, for example to metal, wood, plastic or ceramicmaterials. They are preferably used as topcoat in the finishing ofautomobiles. If the topcoat comprises two layers, of which the lowerlayer is pigmented and the upper layer is not pigmented, the novelcoating composition can be used for either the upper or the lower layeror for both layers, but preferably for the upper layer.

The novel coating compositions can be applied to the substrates by thecustomary methods, for example by brushing, spraying, pouring, dippingor electrophoresis; see also Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 491-500.

Depending on the binder system, the coatings can be cured at roomtemperature or by heating. The coatings are preferably cured at 50-150°C., and in the case of powder coatings or coil coatings even at highertemperatures.

The coatings obtained in accordance with the invention have excellentresistance to the damaging effects of light, oxygen and heat; particularmention should be made of the good light stability and weatheringresistance of the coatings thus obtained, for example paints.

The invention therefore also relates to a coating, in particular apaint, which has been stabilized against the damaging effects of light,oxygen and heat by a content of the compound of the formula F accordingto the invention. The paint is preferably a topcoat for automobiles. Theinvention furthermore relates to a process for stabilizing a coatingbased on organic polymers against damage by light, oxygen and/or heat,which comprises mixing with the coating composition a mixture comprisinga compound of the formula F, and to the use of mixtures comprising acompound of the formula F in coating compositions as stabilizers againstdamage by light, oxygen and/or heat.

The coating compositions can comprise an organic solvent or solventmixture in which the binder is soluble. The coating composition canotherwise be an aqueous solution or dispersion. The vehicle can also bea mixture of organic solvent and water. The coating composition may be ahigh-solids paint or can be solvent-free (e.g. a powder coatingmaterial). Powder coatings are, for example, those described inUllmann's Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages438-444. The additive of present invention can be used therein e.g. asdescribed e.g. in EP-A-856563, especially page 22, line 21, until page26, line 29, and literature cited in this reference.The powder coatingmaterial may also have the form of a powder-slurry (dispersion of thepowder preferably in water).

Examples of resins for powder coatings are:

1. Carboxy- or hydroxy-functionalised polyester resins, based onmonomers such as terephthalic acid, isophthalic acid, neopentyl glycol,2-methyl-1,3-propandiol, tris-1,1,1-(hydroxymethyl)propane etc.

2. Epoxy resins based on bisphenols, such as bisphenol A or Novolac®epoxy resins for thermal or uv-cure with cationic photoinitiators.

3. Hydroxy-, carboxy- or glycidyl-functionalised acrylate polymers andcopolymers. Suitable comonomers include styrene, alkyl methacrylates,acrylamide, acrylonitrile etc.

4. Unsaturated polyester resins for uv-cureable powder coatings,typically used in conjunction with multifuntional vinyl ethers oracrylate esters.

Powder coating based on resins with carboxy functionality are typicallyused together with crosslinking agents of the following classes:

1) polyfunctional epoxy compounds, such as epoxy resins,triglycidylisocyanurate, epoxidised unsaturated fatty acid esters (suchas Uranox® resins from DSM), and esters and ethers of glycidol (such asAraldit® PT910 from Ciba Specialty Chemicals).

2) β-hydroxyalkylamides, such as Primid® types XL552 and QM1260 from EmsChemie. 3) derivatives of melamine, benzoguanimine and glycoluril, suchas Powderlink® 1174 from American Cyanamid.

Crosslinking agents for resins of hydroxy functionality includeanhydrides and especially blocked diisocyanates and uretdiones, etc.

Powder coatings based on resins with epoxy functionality are typicallyused together with crosslinking agents such as diacids (such as1,12-dodecanedioic acid), carboxy-functional polyesters,carboxy-functional copolymers of acrylates and methacrylates, anhydrides(such as the anhydride prepared from 1,12-dodecanedioic acid).

Other additives that can be used together with the compounds of theinvention in powder coatings include: degassing agents, flow promoters,tribocharging additives cure catalysts, sensitisers, cationic andfree-radical photoinitiators, as well as typical liquid paint additives.

A particular advantage of the compounds of the invention is their lowbasicity, as basic compounds often catalyse the crosslinking reactionsof powder coatings to cause poor flow and degassing, and reduced storagestability. This is particularly useful in formulations of highreactivity, such as the glycidylmethacrylate-functionalised acrylics.Here, the combination of the compounds of the invention together withuv-absorbers, especially of the hydroxyphenyltriazine class, can be usedto improve the weatherability without causing catalysis. In other bindersystems and with other classes of uv-absorbers, such as those previouslymentioned to be of particular use in automotive paints, synergisticeffects on the weatherability are also found.

In powder coatings the compounds of the invention can also be used toimprove the oxidative stability and reduce yellowing on curing andoverbaking. Here not only is the low basicity advantageous, but also theability of the hindered morpholinones to withstand and prevent yellowingcaused by oxides of nitrogen in gas-fired ovens. Use togetherparticularly with phosphite and phosphonite costabilisers, as disclosedin EP-A-816442, and dialkylesters of dithiopropionic acid isparticularly beneficial. The compounds of the invention can, whereappropriate also be used to stabilise polyester during manufacture aswell as at all stages of its subsequent use.

The pigments can be inorganic, organic or metallic pigments. The novelcoating compositions preferably contain no pigments and are used as aclearcoat.

Likewise preferred is the use of the coating composition as a topcoatfor applications in the automobile industry, especially as a pigmentedor unpigmented topcoat of the paint finish. Its use for underlyingcoats, however, is also possible.

Some products of present process are novel compounds.

Present invention therefore also pertains to a compound of the formulaI, especially a compound of the formula Ia, wherein R₅, R₆, R₇, R₈ andR₉, independently of each other, are H, C₁ -C₈ alkyl, C₃ -C₈ alkenyl, C₅-C₁₂ aryl, an electron withdrawing group, C₆ -C₁₂ aryl which issubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, and wherein atleast one of R₅, R₆, R₇, R₈ and R₉ is not H. Present invention alsopertains to a compound of the formula I, especially a compound of theformula Ia, wherein R₅, R₆, R₇, R₈ and R₉, independently of each other,are C₁ -C₈ alkyl, C₃ -C₈ alkenyl, C₅ -C₁₂ aryl, an electron withdrawinggroup, C₆ -C₁₂ aryl which is substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen; and all other symbols are as defined above.

Preferred compounds of the formula I are those of the formula Ia##STR44## in which the index n ranges from 1 to 15, being especiallyfrom the range 3-9;

R₅ -R₉ are as defined for formula I; R₁₂ is C₂ -C₁₂ alkylene, C₄ -C₁₂alkenylene, C₅ -C₇ cycloalkylene, C₅ -C₇ cycloalkylene-di(C₁ -C₄alkylene), C₁ -C₄ alkylenedi(C₅ -C₇ cycloalkylene), phenylenedi(C₁ -C₄alkylene) or C₄ -C₁₂ alkylene interrupted by 1,4-piperazinediyl, --O--or >N--X₁ with X₁ being C₁ -C₁₂ acyl or (C₁ -C₁₂ alkoxy)carbonyl orhaving one of the definitions of R₁₄ given below except hydrogen; or R₁₂is a group of the formula (Ib') or (Ic'); ##STR45## with m being 2 or 3,

X₂ being C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which is unsubstituted orsubstituted by 1, 2 or 3 C₁ -C₄ alkyl; phenyl which is unsubstituted orsubstituted by 1, 2 or 3 C₁ -C₄ alkyl or C₁ -C₄ alkoxy; C₇ -C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2or 3 C₁ -C₄ alkyl; and the radicals X₃ being independently of oneanother C₂ -C₁₂ alkylene; the radicals A are independently of oneanother --OR₁₃, --N(R₁₄)(R₁₅) or a group of the formula (Id'); ##STR46##

R₁₃, R₁₄ and R₁₅, which are identical or different, are hydrogen, C₁-C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which is unsubstituted or substituted by1, 2 or 3 C₁ -C₄ alkyl; C₃ -C₁₈ alkenyl, phenyl which is unsubstitutedor substituted by 1, 2 or 3 C₁ -C₄ alkyl or C₁ -C₄ alkoxy; C₇ -C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2or 3 C₁ -C₄ alkyl; tetrahydrofurfuryl or C₂ -C₄ alkyl which issubstituted in the 2, 3 or 4 position by --OH, C₁ -C₈ alkoxy, di(C₁ -C₄alkyl)amino or a group of the formula (Ie'); ##STR47## with Y being--O--, --CH₂ --, --CH₂ CH₂ -- or >N--CH₃, or --N(R₁₄)(R₁₅) isadditionally a group of the formula (Ie'); X is --O-- or >N--R₁₆ ; R₁₆is hydrogen, C₁ -C₁₈ alkyl, C₃ -Cl₈ alkenyl, C₅ -C₁₂ cycloalkyl which isunsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkyl; C₇ -C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2or 3 C₁ -C₄ alkyl; tetrahydrofurfuryl, a group of the formula (If'),##STR48## or C₂ -C₄ alkyl which is substituted in the 2, 3 or 4 positionby --OH, C₁ -C₈ alkoxy, di(C₁ -C₄ alkyl)amino or a group of the formula(Ie'); R₁₁ has one of the definitions given for R₁₆ ; and the radicals Bhave independently of one another one of the definitions given for A;and where in the individual recurrent units of the formula (Ia), each ofthe radicals B, R₁₁ and R₁₂ may have identical or different meanings.

Further new products of present process correspond to formulae IIIc, IVaand Va ##STR49## wherein R is an organic linking group of the formula##STR50##

E₂ is --CO-- or --(CH₂)_(p) --, where p is 0, 1 or 2; E₁ is a carbonatom carrying the two residues R₂₄ and R₂₅, or is >N--R₂₅, or is oxygen,and R₂₄ and R₂₅ are hydrogen or an organic residue, characterized inthat the linking group R in total contains 2-500 carbon atoms and forms,together with the carbon atoms it is directly connected to it and thenitrogen atom, a substituted, 5-, 6 or 7-membered cyclic ring structure;R₁, R₂, R₃ and R₄, independently of each other, are C₁ -C₈ alkyl or C₁-C₅ hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl; R₅, R₆, R₇, R₈and R₉, independently of each other, are H, C₁ -C₈ alkyl, C₂ -C₈alkenyl, C₅ -C₁₂ aryl, C₁ -C₄ haloalkyl, an electron withdrawing group,or C₆ -C₁₂ aryl which is substituted by a residue selected from C₁ -C₄alkyl, C₁ -C₄ alkoxy, halogen; R₂₀ and R₂₁ are halogen; and R₂₂ and R₂₃are hydrogen or together are a chemical bond, with the proviso that R informula IIIc is not the linking group ##STR51## wherein R₂₄ and R₂₅together are ═O or wherein R₂₄ is hydrogen and R₂₅ is hydrogen, OH, oralkanoyloxy which is substituted by phenoxy or alkylphenoxy.

When E₁ is substituted carbon, E₂ mainly is --(CH₂)_(p) --, especiallyCH₂ ; when E₁ is oxygen or NR₂₅, E₂ mainly is carbonyl.

Thus, a compound of formula IIIc, IVa or Va is preferred, wherein R is adivalent C₇ -C₅₀₀ hydrocarbon or a C₂ -C₅₀₀ hydrocarbon containing 1-200hetero atoms selected from nitrogen, oxygen, phosphorus, sulfur, siliconand halogen, and conforms to the structure ##STR52## where p is 0, 1 or2;

R₁, R₂, R₃ and R₄, independently of each other, are C₁ -C₈ alkyl or C₁-C₅ hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl; R₅ and R₆independently are H or methyl; and R₇, R₈ and R₉ independently are C₁-C₄ haloalkyl, phenyl, vinyl, nitro, CN, COOR₁₀, where R₁₀ is C₁ -C₁₂alkyl, C₅ -C₁₂ cycloalkyl or phenyl; R₂₄ and R₂₅ independently arehydrogen or an organic residue as defined, and R₂₆ is hydrogen or anorganic residue forming, together with the remaining structure offormula (VIb) a C₂ -C₅₀₀ hydrocarbon containing 1-200 hetero atomsselected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen.

Most preferred is a compound of formula IIIc, IVa or Va, wherein R₅ andR₆ independently are H or methyl; and R₇, R₈ and R₉ independently are C₁-C₄ bromoalkyl, phenyl, CN, COOR₁₀, where R₁₀ is C₁ -C₁₂ alkyl, C₅ -C₁₂cycloalkyl or phenyl; especially wherein R₅, R₆, R₇, R₈ and R₉ arehydrogen; R₂₀ and R₂₁ are bromo; and when R conforms to the structure offormula VIa, p is 1 and R₁, R₂, R₃ and R₄, independently of each other,are methyl or ethyl; when R conforms to the structure of formula VIb,R₁, R₂, R₃ and R₄, independently of each other, are methyl or ethyl; orR₁ and R₂ together with the carbon atom they are attached to are C₅ -C₁₂cycloalkyl, or R₃ and R₄ together with the carbon atom they are attachedto are C₅ -C₁₂ cycloalkyl; when R conforms to the structure of formulaVIc, R₁, R₂, R₃ and R₄, independently of each other, are C₁ -C₈ alkyl orC₁ -C₅ hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl.

Special emphasis is given to a compound of the formula IIIc ##STR53##wherein R is a C₇ -C₅₀₀ hydrocarbon containing 1-200 hetero atomsselected from nitrogen, oxygen, phosphorus, sulfur and halogen, andforming, together with the two carbon and the nitrogen atom, asubstituted, 5- or 6-membered cyclic ring structure, and R₁, R₂, R₃ andR₄ are as defined above, with the proviso that R does not completeformula IIIc to form a structure of the formula ##STR54##

Especially preferred is a compound of the formula IIIc shown above.Thus, the new sterically hindered amine usually corresponds to theformulae (1a), (1b) or (2a) or contains at least one group of theformula (3) or (4) ##STR55## in which

n₁ is a number from 1 to 4, G and G₁, independently of one another, arehydrogen or methyl, G₁₁ is n-propoxy, O--CH═C═CH₂, O--CH═CH--CH₃ orhalogenated n-propoxy, especially n-propoxy, or brominated n-propoxy;G₁₂, if n₁ is 1, is C₁ -C₁₈ alkyl which is uninterrupted or interruptedby one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalentradical of an aliphatic, cycloaliphatic, unsaturated or aromaticcarboxylic acid, carbamic acid or phosphorus-containing acid or amonovalent silyl radical, preferably a radical of an aliphaticcarboxylic acid having 2 to 18 carbon atoms, of a cycloaliphaticcarboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturatedcarboxylic acid having 3 to 5 carbon atoms, where each carboxylic acidcan be substituted in the aliphatic, cycloaliphatic or aromatic moiety,if present, by 1 to 3 -COOZ₁₂ groups, in which Z₁₂ is H, C₁ -C₂₀ alkyl,C₃ -C₁₂ alkenyl, C₅ -C₇ cycloalkyl, phenyl or benzyl, G₁₂, if n₁ is 2,is C₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, xylylene, a divalent radical ofan aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid,dicarbamic acid or phosphorus-containing acid or a divalent silylradical, preferably a radical of an aliphatic dicarboxylic acid having 2to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acidhaving 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromaticdicarbamic acid having 8-14 carbon atoms, where each dicarboxylic acidmay be substituted in the aliphatic, cycloaliphatic or aromatic moietyby one or two --COOZ₁₂ groups, G₁₂, if n₁ is 3, is a trivalent radicalof an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, whichmay be substituted in the aliphatic, cycloaliphatic or aromatic moietyby --COOZ12, of an aromatic tricarbamic acid or of aphosphorus-containing acid, or is a trivalent silyl radical, and G₁₂, ifn₁ is 4, is a tetravalent radical of an aliphatic, cycloaliphatic oraromatic tetracarboxylic acid; R₁, R₂, R₃ and R₄, independently of eachother, are C₁ -C₈ alkyl or C₁ -C₅ hydroxyalkyl, or R₁ and R₂ togetherwith the carbon atom they are attached to are C₅ -C₁₂ cycloalkyl, or R₃and R₄ together with the carbon atom they are attached to are C₅ -C₁₂cycloalkyl; G is hydrogen or methyl; G₁ and G₂, independently of oneanother, are hydrogen, methyl or together are a substituent ═O; and G₃is a direct bond or methylene, open bonds of formulae (3) and (4) arelinked to a carbon, nitrogen or oxygen atom of an organic residue asdefined above, G₁₃ is hydrogen, C₁ -C₁₂ alkyl, C₂ -C₅ hydroxyalkyl, C₅-C₇ cycloalkyl, C₇ -C₈ aralkyl, C₁ -C₁₈ alkanoyl, C₃ -C₅ alkenoyl,benzoyl or a group of the formula (1b-1) ##STR56## n₂ is the number 1, 2or 3; and G₁₄, if n₂ is 1, is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl,C₅ -C₇ cycloalkyl, C₁ -C₄ alkyl which is substituted by a hydroxyl,cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of theformula --CH₂ --CH(OH)--Z or of the formula --CONH--Z, in which Z ishydrogen, methyl or phenyl; G₁₄, if n₂ is 2, is C₂ -C₁₂ alkylene, C₆-C₁₂ arylene, xylylene, a --CH₂ -CH(OH)--CH₂ group or a --CH₂-CH(OH)--CH₂ --O--D--O-- group, in which D is C₂ -C₁₀ alkylene, C₆ -C₁₅arylene, C₆ -C₁₂ cycloalkylene, or, provided that G₁₃ is not alkanoyl,alkenoyl or benzoyl, G₁₄ can alternatively be 1-oxo-C₂ -C₁₂ alkylene, adivalent radical of an aliphatic, cycloaliphatic or aromaticdicarboxylic acid or dicarbamic acid or alternatively the group --CO--,G₁₄, if n₂ is 3, is a group ##STR57## or, if n₂ is 1, G₁₃ and G₁₄together can be the divalent radical of an aliphatic, cycloaliphatic oraromatic 1,2- or 1,3-dicarboxylic acid.

Preferred new hindered amines of formula Illc are as described above insections (b')-(j') and preferences indicated therein. The new compoundsof formula IIIc are useful as stabilizers for organic material againstdegradation by light, oxygen and/or heat. The materials to be stabilizedcan, for example, be oils, fats, waxes, cosmetics or biocides.Particular interest attaches to use in polymeric materials, as inplastics, rubbers, coating materials, photographic materials oradhesives; examples are organic polymers as described above, andreprographic, especially color photographic material as described, forinstance, in GB-A-2319523, DE-A-19750906, page 23, line 20, until page105, line 32, or in U.S. Pat. No. 5,538,840, column 25, line 60, tocolumn 106, line 31; these parts of U.S. Pat. No. 5,538,840 areincorporated herein by way of reference.

Other preferences are as described above for the compounds of formulae Iand III.

The examples below illustrate the invention further. All parts orpercentages, in the examples as in the remainder of the description andin the claims, are by weight, unless stated otherwise. Room temperaturedenotes a temperature in the range 20-30° C., unless stated otherwise.In the examples, the following abbreviations are used:

    ______________________________________                                        m.p.       melting point or range;                                              Mn number average of molecular weight (g/mol);                                Mw weight average of molecular weight (g/mol);                                GPC gel permeation chromatography.                                          ______________________________________                                    

EXAMPLE 1

Preparation of the starting compound of the formula ##STR58##

Step 1: A solution of 74.3 g (0.35 moles) ofN-(2,2,6,6-tetramethyl-4-piperidinyl)-n-butylamine in 50 ml of water isadded slowly at 0° C. to a solution of 64.5 g (0.35 moles) of cyanuricchloride in 500 ml of xylene, keeping the temperature during theaddition and for further 1 hour. After 2 hours at room temperature, themixture is cooled to 0° C. and an aqueous solution of 14.7 g (0.368moles) of sodium hydroxide in 50 ml of water is added. After 1/2 hour at0° C. and for further 2 hours at room temperature, the aqueous solutionis separated off and 69.2 g (0.175 moles) ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine are added.

The mixture is heated to 50° C. for 1 hour and 48.4 g (0.35 moles) ofground potassium carbonate are added and heated to 60° C. for 4 hours.

After washing with water, the organic phase is concentrated under vacuumat 60°-70° C./10 mbar, being 250 ml of xylene recovered. 138.1 g (0.35moles) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamineare added and the mixture is heated to 150° C. for 2 hours, cooled againand added with 14 g (0.35 moles) of ground sodium hydroxide.

The mixture is heated to 140° C. for further 4 hours, being the residualwater of reaction eliminated off azeotropically and for further 4 hoursat 160° C.

After cooling to 60° C., the mixture is diluted with 300 ml of xylene,filtered and washed three times with 100 ml of ethylene glycol.

This solution can be used for the isolation of the compound described inExample 6.

Step 2: After concentrating under vacuum at 60° C./10 mbar, 54.4 g(0.147 moles) of 2-chloro-4,6-bis-(dibutylamino)-1,3,5-triazine areadded.

The mixture is heated to 140° C. for 3 hours and 20.3 g (0.147 moles) ofground potassium carbonate are added, being the mixture heated to refluxand being the reaction water eliminated off azeotropically.

The mixture is heated to 160° C. for 4 hours, added to further 20.3 g(0.147 moles) of ground potassium carbonate and heated again to 160° C.for 2 hours. After cooling to 60° C., the mixture is diluted with 300 mlof xylene, filtered and concentrated under vacuum at 140° C./1 mbar. Asolid is obtained with a melting range of 130-136° C. after drying; Mn(bv GPC): 2830 g/mol.

EXAMPLE 2

Process of present invention; preparation of the compound of the formula##STR59##

Step 1: In a 1 liter stainless steel autoclave with heating andmechanical stirrer are charged: a solution of 150 g (0.05 mol) of theproduct of example 1 in 400 ml of xylene, 66.5 g (0.55 mol) of allylbromide and 114 g (0.825 mol) of potassium carbonate. The mixture isheated to 150° C., left to react for 5 hours and cooled down to 60° C.300 ml of water are added and the mixture is vigorously stirred. Theorganic layer is then collected and charged in a 1 liter round bottomedflask equipped with a mechanical stirrer, thermometer and droppingfunnel. After cooling to -15° C., 128 g of a solution of 32% by weightof peracetic acid in acetic acid is added during 30 minutes understirring. The temperature is raised to 0° C. and the reaction mixture isleft to react for 4 hours.

A solution of 250 g of K₂ CO₃ in 500 ml of water is added and kept for30 minutes at 0° C. with stirring. The organic layer is collected,washed 3 times with 100 ml portions of water, and dried over sodiumsulfate.

Step 2: The solution is charged in a 1 l stainless steel autoclave.After addition of 3 g of 5% by weight platinum on carbon, the autoclaveis filled with hydrogen of 40 bar and maintained at 70° C. with stirringfor a period of 6 hours. Subsequently, the autoclave is cooled to 20° C.and vented. After removing the catalyst by filtration, the solution isconcentrated at 140° C. and 1 mbar. The product is obtained as a whitesolid, m.p. 127°-135° C., Mn (GPC)=3580 g/mol, Mw/Mn=1.33.

EXAMPLE 3

Process of present invention; preparation of the compound of the formula##STR60## In a round bottomed flask are charged: 20 g of1allyl-2,2,6,6-tetramethyl-piperidin-4-ol, 40 ml of methanol, 118 g ofH₂ O₂ solution at 35% (v/v). The mixture is heated to 65° C., left toreact for 5 hours, concentrated under vacuum until methanol has beendistilled off and 40 ml of CH₂ Cl₂ are added. The mixture is stirred andthe organic layer is collected and concentrated. The product is obtainedas a pale yellow oil.

¹ H NMR (300 MHz, CDCl3)/ppm: 5.90-5.80 (m, 1 H); 5.21-4.97 (m, 2 H);4.24 (m, 2 H); 3.87 (m, 1 H); 1.75 (m, 2 H); 1.42 (m, 2 H); 1.15 (s, 3H); 1.11 (s, 3 H).

EXAMPLE 4a

Preparation of the compound of the formula ##STR61## In a stainlesssteel autoclave are charged : 20 g of the product of example 3, 0.2 g ofnickel raney and 100 ml of toluene; the autoclave is filled withhydrogen of 8 bar and maintained at 25° C. under stirring for a periodof 8 hours. Subsequently the autoclave is vented , the catalyst isremoved by filtration and the mixture is concentrated under vacuum. Theproduct is obtained as a white solid.

¹ H NMR (300 MHz, CDCl3)/ppm: 3.95 (m,1 H); 3.66 (t, 2 H); 1.57 (m, 4H); 1.22 (m, 2 H); 1.13 (s, 12 H); 0.89 (t, 3 H).

EXAMPLE 4b

Preparation of the compound of the formula ##STR62## In a round bottomedflask are charged: 20 g of product of example 4a), 10.6 g of methylsebacate, 100 ml of xylene and 0.25 g of di-butyl-tin-oxide. The mixtureis heated to 145° C., left to react for 6 hours with stirring, cooleddown and concentrated under vacuum, yielding the above product as anoil.

¹ H NMR (300 MHz, CDCl3)/ppm: 4.95 (m, 2 H); 3.66 (t, 4 H); 2.21 (t, 4H); 1.77 (m, 4 H); 1.63-1.42 (m, 12 H); 1.28-1.18 (m, 36 H); 0.90 (t, 6H).

Other analytical data:

    ______________________________________                                        HPLC assay: 80%                                                                 Elemental analysis:                                                            C measured 67.6% calculated 68.4%                                             H measured 10.6% calculated 10.8%                                             N measured 4.7% calculated 4.7%                                            ______________________________________                                    

EXAMPLE 5

Process of present invention; preparation of the compound of the formula##STR63## In a stainless steel autoclave are charged 20 g of sebacicacid bis-(2,2,6,6-tetramethylpiperidin-4yl) ester (commercial name:Tinuvin® 770), 24 g of allyl bromide, 6 g of potassium carbonate and 100ml of toluene; the mixture is heated to 120° C., left to react for 5hours with stirring, cooled down and filtered to remove the salts. Theexcess of allyl bromide is removed by distillation.

The solution is charged in a round bottomed flask and 8 g ofmetachloroperbenzoic acid dissolved in 50 ml of toluene are added over aperiod time of 30 minutes keeping the temperature below 25° C.

Then a solution of 13 g of potassium carbonate in 100 ml of water isadded to the reaction mixture and it is left under stirring for 30minutes. The organic layer is collected and washed with a potassiumcarbonate solution prepared as described above. The organic layer isthen dried over sodium sulfate and charged in a stainless steelautoclave. After addition of 1 g of 5% by weight platinum on carbon, theautoclave is filled with hydrogen of 8 bar and maintained at 25° C. withstirring for 4 hours. After removing the catalyst by filtration, thesolution is concentrated under vacuum. The product is obtained as a paleyellow oil;

¹ H NMR (300 MHz, CDCl3)/ppm: 4.95 (m, 2H); 3.66 (t, 4H); 2.21 (t, 4H);1.77 (m, 4H); 1.63-1.42 (m, 12 H); 1.28-1.18 (m, 36 H); 0.90 (t, 6 H).

Other analytical data:

    ______________________________________                                        HPLC assay: 78%                                                                 Elemental analysis:                                                            C measured 67.2% calculated 68.4%                                             H measured 10.3% calculated 10.8%                                             N measured 4.6% calculated 4.7%                                            ______________________________________                                    

EXAMPLE 6

Intermediate of the formula ##STR64##

The preparation of the current compound follows the procedure describedin Example 1 up to Step 1. The solution obtained from step 1 is thenconcentrated at 140°C. and 1 mbar and it yields a solid, mp 138-143° C.,with an average Mn (by GPC) of 2555 g/mol.

EXAMPLE 7 ##STR65##

To a solution of 150 g of the product of example 6 in 400 ml of xyleneare added 66.5 g of allyl bromide and 114 g of potassium carbonate. Themixture is heated to 150° C., left to react for 5 hours and cooled downto 60° C. 300 ml of water are added and the mixture is vigorouslystirred. The organic layer is then collected, cooled to -15° C. and 128g of a solution of 32% by weight of peracetic acid in acetic acid isadded during 30 minutes under stirring. The temperature is raised to 0°C. and the reaction mixture is left to react for 4 hours. A solution of250 g of K₂ CO₃ in 500 ml of water is added while stirring and left toreact for 30 minutes at 0° C. The organic layer is collected, washed 3times with 100 ml portions of water, and dried over sodium sulfate. Thesolution is charged in a 1 l stainless steel autoclave. After additionof 3 g of 5% by weight platinum on carbon, the autoclave is filled withhydrogen of 40 bar and maintained at 70° C. with stirring for a periodof 6 hours. Subsequently, the autoclave is cooled to 20° C. and vented.After removing the catalyst by filtration, the solution is concentratedat 140° C. and 1 mbar. The product is obtained as a white solid, m.p.125-135° C., Mn (GPC)=2979 g/mol.

EXAMPLE 8

Compound of the formula ##STR66##

To a solution of 93 g of2-chloro-4,6-bis-(N-n-butyl-N-(2,2,6,6-tetramethylpiperidin-4-yl))-1,3,5-triazinein 300 ml of toluene are added 42 g of allyl bromide and 71.7 g ofpotassium carbonate. The mixture is heated to 150° C., left to react for10 hours, cooled down to 60° C. and 300 ml of water are added whilestirring. The organic layer is then collected and cooled to -5° C., 64 gof a solution of 39% by weight of peracetic acid in acetic acid is addedduring 30 minutes under stirring. The temperature is raised to 0C andthe reaction mixture is left to react for 2 hours.

A solution of 90 g of sodium carbonate in 500 ml of water is added andkept for 30 minutes at 0° C. with stirring. The organic layer iscollected and dried over sodium sulfate. The solution is charged in a 1l stainless steel autoclave. After addition of 3 g of 5% by weightplatinum on carbon, the autoclave is filled with hydrogen of 40 bar andmaintained at 70° C. with stirring for a period of 6 hours.Subsequently, the autoclave is cooled to 20° C. and vented. Afterremoving the catalyst by filtration, the solution is concentrated at140° C. and 1 mbar. The product is obtained as a white solid.

1 H NMR (300 MHz, CDCl3)/ppm: 4.97 (m, 2 H) ; 3.67 (t, 4 H) ; 3.29 (m, 4H); 1.80-1.30 (m, 20 H); 1.31-1.08 (m, 28 H); 0.92-0.80 (m, 12 H).

EXAMPLE 9

Compound of the formula ##STR67##

A mixture composed of 64.5 g of the compound described in the example 8,200 ml of xylene, 20.4 g of potassium carbonate and 4.6 g ofN-1-[2-(3-Amino-propylamino)-ethyl]-propane-1,3-diamine is heated up to140° C. for 10 hours, cooled down to 20° C. and washed with 200 ml ofwater. The collected organic layer is concentrated at 140° C. and 1mbar. The solid obtained has a m.p. in the range of 115-120°C.

EXAMPLE 10

Compound of the formula ##STR68##

To a solution of 30 g ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine in 240 mlof toluene are added 50 g of allyl bromide and 63 g of potassiumcarbonate. The resulting mixture is heated up to 150° C. and left toreact for 6 hours, cooled down to 20° C., filtered and the volume of thesolution is reduced at 100 ml by solvent evaporation at 110° C. and 1mbar of vacuum. To the concentrate solution are added 150 ml of toluene,after cooling down to -10° C. a solution of 82 g of m-chloro perbenzoicacid in 200 ml of toluene is added over one hour under stirring. Afterheating the mixture up to 0° C., a solution of 100 g of potassiumcarbonate in 300 ml of water is added under stirring and left to reach20° C.

The organic layer is collected, dried over sodium sulfate andhydrogenated with 40 bar of hydrogen with 2 g of 5% platinum over carbonat 70° C. for 8 hours. The catalyst is recovered by filtration and thesolution is concentrated at 110° C. under 1 mbar.

1 H NMR (300 MHz, CDCl3)/ppm: 3.75 (t, 4 H) ; 3.54 (t, 4 H); 2.82 (m, 2H); 2.63 (t, 4H); 1.78-1.45 (m, 20 H) ; 1.42-1.23 (m, 4 H); 1.16 (s, 12H); 1.10 (s, 12 H), 0.89 (m, 6 H).

EXAMPLE 11

Compound of the formula ##STR69##

To a solution of 90 g of benzoic acid 1-but-2-enyl-2,2,6,6-tetramethyl-piperidin-4-yl ester in 200 ml oftoluene, are added 70 g of 4-Bromo-2-butene and 100 g of potassiumcarbonate. The mixture is heated to 140° C., left to react for 10 hoursunder stirring, cooled down to 20° C., poured in 200 ml of water andstirred. The organic layer is then collected, concentrated by removing100 ml solvent at 110° C. at 20 mbar, then added with 100 ml of freshtoluene. The resulting solution is cooled down to -150° C. and asolution of 100 g of m-chloro-perbenzoic acid in 200 ml of toluene isadded during 30 minutes under stirring. The mixture is left to react for2 hours at 0° C. then a solution of 40 g of potassium carbonate in 300ml of water is added under stirring. The organic layer is collected andthe solvent evaporated under vacuum. The product obtained is a paleyellow liquid.

1 H NMR (300 MHz, CDCl3)/ppm: 7.99 (d, 2 H); 7.49 (m, 1 H) ; 7.37 (m, 2H); 5.85 (m, 1 H); 5.26 (m,1 H); 5.06-5.00 (m, 2 H); 4.28 (m, 1 H); 1.94(m, 2 H) ;1.71 (m, 2 H); 1.25-1.17 (m, 15 H).

EXAMPLE 12

Compound of the formula ##STR70##

To a solution of 52 g of 2,2,6,6, tetramethylpiperidine in 250 ml ofhexane are added 102 g of potassium carbonate and 135 g of propargylbromide. The mixture is heated to 140° C., left to react for 10 hoursunder stirring, cooled down to 20° C., poured in 300 ml of water andstirred. The organic layer is then collected, dried over sodiumsulphate, and distilled under vacuum collecting the fraction at 64° C.and 10 mmHg which is then dissolved in 250 ml of dichloromethane andcooled to -15° C. To the resulting solution is added a solution of 100 gof m-chloro-perbenzoic acid in 200 ml of hexane in 30 minutes whilestirring. The mixture is left to react for 2 hours at 0° C. and asolution of 40 g of potassium carbonate in 300 ml of water is addedwhile stirring. The organic layer is collected, dried over sodiumsulfate and the solvent evaporated under vacuum. The product obtained isa pale yellow liquid.

1 H NMR (300 MHz, CDCl3)/ppm: 6.82 (t, 1 H); 5.49 (d, 2 H) ; 1.52 (s, 6H); 1.13 (s, 12 H). ##STR71##

EXAMPLE 13

Compound of the formula

A mixture of 16 g of the compound described in the example 11, 500 ml ofethanol and 0.9 g of Lindlar catalyst is charged in an autoclave. Theautoclave is filled with 10 bar of hydrogen and maintained at 40° C.under stirring for a period of 6 hours, then it is cooled to 20° C. andvented. After removing the catalyst by filtration, the solution isconcentrated under vacuum. The resulting product is obtained as a paleyellow liquid.

1 H NMR (300 MHz, CDCl3)/ppm: 6.29 (d, 1 H); 4.01 (m, 1 H); 1.57 (d, 3H); 1.45 (m, 6 H); 1.12 (s, 12 H).

EXAMPLE 14

Compound of the formula ##STR72##

A mixture of 38 g of the compound described in the example 11, 300 ml oftoluene and 1 g of platinum supported on carbon at 5% by weight ischarged in an autoclave. The autoclave is filled with 30 bar of hydrogenand maintained at 40° C. under stirring for a period of 6 hours, then itis cooled to 20° C. and vented. After removing the catalyst byfiltration, the solvent is removed by vacuum concentration at 110° C.and 35 mbar. The resulting product is obtained as a pale yellow liquid.

1 H NMR (300 MHz, CDCl3)/ppm: 3.69 (t, 2 H); 1.45 (m, 8 H); 1.15 (s, 12H) ; 0.92 (t, 3 H).

EXAMPLE 15

Compound of the formula ##STR73##

207 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine, 100 g of DBE-2° (amixture of 75% of glutaric acid dimethyl ester and 25% of adipic aciddimethyl ester, from DuPont-USA) are dissolved in 500 ml of toluene,added with 2 g of lithium amide and heated and maintained to reflux for6 hours, while the methanol formed during the reaction is distilled offby azeotropation. The mixture is then cooled to 20° C., washed withwater, dried over sodium sulfate. The resulting solution is then reactedwith allyl bromide, sodium carbonate, peracetic acid, hydrogen and 5% byweight platinum on carbon, following the same procedure and the samestoichiometric ratios described for the preparation of the compound inexample 5. The product is obtained as a pale yellow oil.

1 H NMR (300 MHz, CDCl3)/ppm: 4.95 (m, 2 H); 3.63 (t, 4 H); 2.24 (m, 2H); 1.86-1.71 (m, 4 H-6 H); 1.57-1.44 (m, 8 H); 1.15 (m, 28 H); 0.89 (m,6 H).

EXAMPLE 16

Compound of the formula ##STR74##

Step 1: To a solution of 64 g of2,4,6-tris-(N-n-butyl-N-(2,2,6,6-tetramethylpiperidin-4-yl))-1,3,5-triazinein 300 ml of toluene are added 48 g of allyl bromide and 55.8 g ofpotassium carbonate. The mixture is heated to 150° C., left to react for5 hours, cooled down to 60° C. and 300 ml of water are added whilestirring. The organic layer is then collected, concentrated by removing100 ml of solvent at 110° C. at 20 mbar, added with 400 ml of freshtoluene, cooled to -5° C. and 57 g of a solution of 39% by weight ofperacetic acid in acetic acid is added during 30 minutes under stirring.The temperature is raised to 0° C. and the reaction mixture is left toreact for 2 hours.

A solution of 80 g of sodium carbonate in 500 ml of water is added andkept for 30 minutes at 0° C. with stirring. The organic layer iscollected and dried over sodium sulfate.

Step 2: The solution is charged in a 1 l stainless steel autoclave.After addition of 2 g platinum supported on carbon at 5% by weight, theautoclave is filled with hydrogen of 40 bar and maintained at 70° C.with stirring for a period of 6 hours, then cooled to 20° C. and vented.After removing the catalyst by filtration, the solution is concentratedat 140° C. and 1 mbar. The product is obtained as a white solid, m.p.92-100° C.

EXAMPLE 17

Compound of the formula ##STR75##

The solution obtained in step 1 of example 14 is added with 43 g ofbromine in 30 minutes while stirring at 25° C. in the dark. The mixtureis left to react for 6 hours at 25° C., washed with a solution of 54 gof potassium carbonate in 500 ml of water, collected, dried with sodiumsulfate and concentrated at 100° C. under reduced pressure (10 mbar).The obtained pale pink solid has a melting point 106-110° C.

EXAMPLE 18

Compound of the formula ##STR76##

To the solution obtained in step 1 of example 2, 88 g of bromine isadded during 30 minutes while stirring at 25° C. in the dark. Themixture is left to react for 6 hours at 25° C., washed with a solutionof 108 g of potassium carbonate in 1000 ml of water, collected, driedwith sodium sulfate and concentrated at 120° C. under reduced pressure(10 mbar). The obtained pale yellow solid has a melting point higherthan 250° C. (decomposition).

Bromine content: 32.1% by weight; Mn (by GPC): 2862.

Application Examples EXAMPLE 20 LIGHT STABILIZING ACTION IN PP TAPES

1 g of each compound of the list reported below and, 1 g oftris(2,4-di-ter-butylphenyl) phosphite, 0.5 g of pentaerythritoltetrakis (3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate) , 1 g ofcalcium stearate are mixed in a turbomixer with 1000 g of polypropylenepowder having a melt index of 2.1 gl 10 minutes (measured at 230° C. and2.16 Kg) and already containing 1 g of tris(2,4-di-ter-butylphenylphosphite) and 10.5 g of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate).

The mixture is extruded at 200-220° C. to give polymer granules whichare subsequently converted to stretched tapes of 50 microns thicknessand 2.5 mm width, using a semi industrial type of apparatus(Leonard-Sumirago(VA)-Italy) and working under the following conditions:

Extruder temperature: 210-230° C.

Head temperature: 240-260° C.

Stretch ratio: 1:6

The tapes thus prepared are mounted on a white card and exposed inWeather-O-Meter 65 WR (ASTM G26-96D 2565-85) with a black paneltemperature of 63° C.

The residual tensile strength is measured, by means of a constantvelocity tensometer, on a sample taken after various light exposuretimes; from this, the exposure time (in hours) required to halve theinitial tensile strength (T50) is calculated.

For the purpose of comparison, tapes prepared under the same conditionsas indicated above, but without the addition of the stabilisers of thepresent invention, are exposed.

The results obtained are shown in the table below.

    ______________________________________                                        Compound of the Invention                                                                        T50 (hours)                                                ______________________________________                                        none               340                                                          compound of example 5 3040                                                  ______________________________________                                    

EXAMPLE 21 LIGHT STABILIZING ACTION IN LDPE FILMS

Each compound of the list reported below is mixed via master batch withLDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy),characterised by a density of 0.921 g/cm³ and a melt flow index (190°C./2.16 Kg) of 0.60 g/10 minutes, in a slow mixer. The master batch hadpreviously been prepared by extruding powdered LDPE and 10% by weight ofthe compounds of the list reported below.

The mixture is blow extruded at 210° C. and films of 150 micronsthickness are obtained.

Films are mounted on a white cardboard in metal frames and exposed inAtlas Ci 65 Xenon Arc Weather-O-meter, at 63° C. black paneltemperature, continues dry cycle, according to ASTM G 26-96.

During the exposure, the performance is periodically evaluated measuringthe carbonyl increment (iCO; increase of carbonyl concentration) bymeans of a FT-IR spectrophotometer and testing the samples forembrittlement. For some samples, the residual tensile strength ismeasured by means of a constant velocity tensometer, on a sample takenafter various light exposure times; from this, the exposure time (inhours) required to halve the initial tensile strength (T50) iscalculated.

Results are compiled in the following table; a low increase of carbonylconcentration and a high T50 time indicate good stabilisation.

                  TABLE                                                           ______________________________________                                        Increase of carbonyl concentration (iCO)                                        after 4760 hours exposure and T50                                               Compound     T50/hours    iCO                                             ______________________________________                                        0.2% of example 2                                                                          >7050        0.08                                                  without stabiliser 660 embrittled after 1560 h                              ______________________________________                                    

EXAMPLE 22 LIGHT STABILIZING ACTION IN LDPE FILMS TREATED WITH BORDEAUXMIXTURE

Each compound of the list reported below is mixed via master batch withLDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy),characterised by a density of 0.921 g/cm³ and a melt flow index (190°C./2.16 Kg) of 0.60 g/10 minutes, in a slow mixer.

The master batch had previously been prepared by extruding powdered LDPEand 10% by weight of the compound of the list reported below.

The mixture is blow extruded at 210° C. and films of 150 micronsthickness are obtained.

Films for pesticide treatment are kept 24 hours in a suspension ofBordeaux mixture (widely used pesticide based on copper sufate) andwater (10 g of mixture in 1 liter of water).

Treated films are put into quartz tubes and are exposed in Atlas Ci 65Xenon Arc Weather-O-meter, at 63° C. black panel temperature, continuosdry cycle, according to ASTM G 26-96.

During the exposure, the performance is periodically evaluated measuringthe carbonyl increment (increase of carbonyl concentration; iCO) bymeans of a FT-IR spectrophotometer. Results are compiled in thefollowing table.

                  TABLE                                                           ______________________________________                                        Increase of carbonyl concentration (iCO)                                        after indicated hours of weathering                                                 Compound     iCO after 0 h                                            ______________________________________                                        0.15% of example 2                                                                             0                                                              without stabiliser 0                                                        ______________________________________                                    

EXAMPLE 23 LIGHT STABILIZING ACTION IN LDPE FILMS TREATED WITH VAPAM

Each compound of the list reported below is mixed via master batch withLDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy),characterised by a density of 0.921 g/cm³ and a melt flow index (190°C./2.16 Kg) of 0.60 g/10 minutes, in a slow mixer.

The master batch had previously been prepared by extruding powdered LDPEand 10% by weight of the compound of the list reported below.

The mixture is blow extruded at 210° C. and films of 150 micronsthickness are obtained.

Films for pesticide treatment are kept inside a dryer for 20 days at 30°C., in presence of the vapours emitted by 2 lt of an aqueous solutioncontaining 50% of VAPAM (Baslini S.p.A., Treviglio/BG, Italy), which, inturn, in an aqueous solution of 382 g per litre of metam-sodium, havingthe formula CH₃ --NH--CS--SNa.

Treated films are put into quartz tubes and are exposed in Atlas Ci 65Xenon Arc Weather-O-meter, at 63° C. black panel temperature, continuosdry cycle, according to ASTM G 26-96.

During the exposure, the performance is periodically evaluated measuringthe carbonyl increment by means of a FT-IR spectrophotometer and testingthe samples for embrittlement. Results are compiled in the followingtable; a low increase of carbonyl concentration indicates goodstabilisation.

                  TABLE                                                           ______________________________________                                        Increase of carbonyl concentration (iCO) after 1000 hours exposure                 Compound    Concentration  iCO                                           ______________________________________                                        example 2    0.2%           0.38                                                without stabiliser 0 embritteled                                            ______________________________________                                    

EXAMPLE 24 LIGHT STABILIZING ACTION IN GREENHOUSE FILMS

Each compound of the list reported below is mixed via master batch withLDPE pellets (Riblene FF 29, supplied by Enichem, Milano, Italy),characterised by a density of 0.921 g/cm³ and a melt flow index (19°C./2.16 Kg) of 0.60 g/10 minutes, in a slow mixer.

The master batch had previously been prepared by extruding powdered LDPEand 10% by weight of the sterically hindered hydroxylamine ether ofpresent invention (compound A) and the relevant concentrations ofcomponent B (=oxo and or hydroxyl group containing metal costabiliser)and C (further costabiliser; salt of carboxylic acid).

The mixture is blow extruded at 210° C. and films of 150 micronsthickness are obtained. The films are exposed on the south face roof ofa greenhouse in Pontecchio Marconi (Bologna-Italy). The followingpesticide are applied in the greenhouse:

VAPAM (Baslini S.p.A., Treviglio/BG, Italy), which, in turn, in anaqueous solution of 382 g per liter of metam-sodium, having the formulaCH₃ --NH--CS--SNa; SESMETRIN (Bimex SpA, Isola/VI, Italy), which is a23.75% (% w/w) aqueous solution of permethrin having the formula##STR77##

The greenhouse is treated with a solution of 4 liters of VAPAM in 10liters of water every 6 months, and with SESMETRIN (5 g in 5 liters ofwater) every month.

During the exposure, the performance is periodically evaluated measuringthe carbonyl increment by means of a FT-IR spectrophotometer. Theexposure is measured in kilolangley (Klys; energy per unit area); 1100Klys corresponds to 1 year of exposure.

    ______________________________________                                        Compound A  Component B Ca-Stearate                                                                              iCO after                                  ______________________________________                                        0, 4% of example 2                                                                        0.2% ZnO    0.2                                                     0, 4% of example 2 0 0                                                        none 0 0                                                                    ______________________________________                                    

EXAMPLE 25

Wood Coating

a) Impregnation:

The substrate (pine) is impregnated using a a commercially availableimpregnation ("Xylamon® Incolore" solids content of 5,2% from Sepam).

The impregnation is applied by brush (1 application) and dried for 24hours at room temperature.

b) Top Coat:

A top coat is prepared from:

73.8 parts of an Alkyd Resin (Jagol PS 21 ®, E. Jager KG),

0.52 parts of antiskinning agent (Exkin 2®, Servo Delden B. V.)

20.8 parts of aliphatic hydrocarbon solvent (Exxsol D 40®, DeutscheExxon Chemical GmbH)

4.16 parts of a metal drier (Jager Antihydro--Trockner®, E. Jager KG)

0,70 parts of a PE--wax, 21% in solvent (Lanco Glidd AH® , G. M. Langer& Co)

The top coat is stabilized with 2% UVA (compound of the formula##STR78##

UV-Absorber from Ciba Specialty Chemicals) and 1% stabilizer accordingto the invention as indicated in the following table. All concentrationsare by weight based on binder solids.

The topcoat is applied by brush (2 applications) on the impregnated pinepanels and dried for 24 hours at room temperature after eachapplication. The panels are exposed to accelerated weathering: (QUV, 8 hlight at 70° C., 4 h condensation at 50° C., UV--A lamps). Gloss (60°)is measured according to DIN 67530 every 400h weathering. An unexposedpine panel with unstabilized top coat is used as reference. The resultsare presented in the following table.

                  TABLE                                                           ______________________________________                                        Gloss (60°) after 2400 h exposure                                      ______________________________________                                        Unstabilized Topcoat  25                                                        2% UVA 63                                                                     2% UVA + 1% cpd. of example 5 86                                            ______________________________________                                    

Initial gloss (60°) for all samples: 92-93

The results show a good gloss retainment achieved with the stabilizer ofpresent invention.

EXAMPLE 26

Stabilization of a 2-coat metallic finish

The light-stabilizers to be tested are dissolved in 30 g of Solvesso®100and tested in a clearcoat having the following composition (parts byweight):

    ______________________________________                                        Synthacryl ® SC 303.sup.1)                                                                      27.51                                                     Synthacryl ® SC 370.sup.2) 23.34                                          Maprenal ® 650.sup.3) 27.29                                               Butyl acetate/Butanol (37/8) 4.33                                             Isobutanol 4.87                                                               Solvesso ® 150.sup.4) 2.72                                                Crystal Oil K-30.sup.5) 8.74                                                  Levelling assistant Baysilon ® MA.sup.6) 1.20                              100.00                                                                     ______________________________________                                         .sup.1 Acrylate resin,  ®Hoechst AG; 65% solution in xylene/butanol       (26:9)                                                                        .sup.2 Acrylate resin,  ®Hoechst AG; 75% solution in Solvesso ®       100.sup.4                                                                     .sup.3 Melamine resin,  ®Hoechst AG; 55% solution in isobutanol           .sup.4 aromatic hydrocarbon mixture, boiling range 182-203° C.         (Solvesso ® 150) or 161-178° C. (Solvesso ® 100);              manufacturer:  ®Esso                                                      .sup.5 aliphatic hydrocarbon mixture, boiling range: 145-200° C.;      manufacturer:  ®Shell                                                     .sup.6 1% in Solvesso ® 150; manufacturer:  ®Bayer AG            

1% of the stabilizer indicated in the following table and 1.5% of theUVA of example 25 are added to the clearcoat, based on the solidscontent of the varnish. For comparison, a clearcoat containing nolight-stabilizers is used. The clearcoat is diluted with Solvesso® 100to spray viscosity and is applied by spraying to a prepared aluminiumpanel (®Uniprime Epoxy, silver-metallic basecoat) which is baked at 130°C., for 30 minutes, to give a dry film thickness of 40-50 μm ofclearcoat.

The samples are then weathered in an Atlas Xe-Wom weatherometer (CAM180) in a cycle as follows: 40' UV-light, 20' light with rain (front),60' light, 60' dark with rain (both sides), light at 70° C., dark at 40°C. (Filter: quartz/boro; 0.55 W/cm² at 340 nm).

The surface gloss (20° gloss as defined in DIN 67530) of the samples isthen measured at regular intervals; high values indicate a goodstabilization. The results are shown in the following table.

                  TABLE                                                           ______________________________________                                                     20° gloss (DIN 67530)                                        after . . . hours weathering                                               Light-stabilizer                                                                           0 hours   800 hours                                                                              3200 hours                                    ______________________________________                                        None         94        33       crack after 800 h                               1% cpd. of example 5 + 92 92 72                                               1.5% UVA                                                                    ______________________________________                                    

What is claimed is:
 1. A process for the preparation of a compound ofthe formula (I) ##STR79## wherein R₁, R₂, R₃ and R₄, independently ofeach other, are C₁ -C₈ alkyl or C₁ -C₅ hydroxyalkyl, or R₁ and R₂together with the carbon atom they are attached to are C₅ -C₁₂cycloalkyl, or R₃ and R₄ together with the carbon atom they are attachedto are C₅ -C₁₂ cycloalkyl;R₅, R₆, R₇, R₈ and R₉, independently of eachother, are H; C₁ -C₈ alkyl; C₂ -C₈ alkenyl; C₅ -C₁₂ aryl; C₁ -C₄haloalkyl; an electron withdrawing group selected from the groupconsisting of CN, nitro, halogen and --COOR₁₀, where R₁₀ is C₁ -C₁₂alkyl or C₅ -C₁₂ cycloalkyl or C₇ -C₉ phenylalkyl or phenyl; or R₅, R₄.R₇, R₈ and R₉, independently of each other, are C₆ -C₁₂ aryl which issubstituted by a residue selected from C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen; and R₇ and R₈ together may also form a chemical bond; and thelinking group R forms, together with the carbon atoms it is directlyconnected to and the nitrogen atom, a substituted, 5-, 6 or 7-memberedcyclic ring structure; wherein a compound of the formula (II) ##STR80##wherein all residues R and R₁ -R₉ are as defined for formula (I), isoxidized.
 2. A process according to claim 1, wherein the oxidationreaction is carried out in the presence of a solvent and an oxidantselected from oxygen, peroxides, nitrates, permanganates and chlorates.3. A process according to claim 1 for the preparation of a compound offormula (I) by oxidation of a compound of formula (II),wherein R₁, R₂,R₃ and R₄, independently of each other, are C₁ -C₈ alkyl or C₁ -C₅hydroxyalkyl, or R₁ and R₂ together with the carbon atom they areattached to are C₅ -C₁₂ cycloalkyl, or R₃ and R₄ together with thecarbon atom they are attached to are C₅ -C₁₂ cycloalkyl; R₅, R₆, R₇, R₈and R₉, independently of each other, are H, C₁ -C₈ alkyl, C₃ -C₈alkenyl, C₅ -C₁₂ aryl, an electron withdrawing group selected from thegroup consisting of CN, nitro, halogen and --COOR₁₀, where R₁₀ is C₁-C₁₂ alkyl or C₅ -C₁₂ cycloalkyl or C₇ -C₉ phenylalkyl or phenyl; or R₅,R₆, R₇, R₈ and R₉, independently of each other, are C₆ -C₁₂ aryl whichis substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen; and R formstogether with the two carbon atoms and the nitrogen atom, a substituted,6-membered cyclic ring structure.
 4. A process according to claim 1,wherein in the compounds of formulae (I) and (II)R₁, R₂, R₃ and R₄independently preferably are methyl or ethyl, R₅ and R₆ independentlyare H or methyl, and R₇, R₈ and R₉ independently are C₁ -C₄ haloalkyl,phenyl, vinyl, nitro, CN, COOR₁₀, or R₇ and R₈ together form a chemicalbond.
 5. A process for the preparation of a compound of the formula (V)##STR81## wherein R, R₁, R₂, R₃ and R₄, R₅, R₆, and R₉ are as definedfor formula (I) in claim 1,R₇ and R₈ are H, C₁ -C₈ alkyl, C₃ -C₈alkenyl, C₅ -C₁₂ aryl, C₁ -C₄ haloalkyl, an electron withdrawing groupselected from the group consisting of CN, nitro, halogen and --COOR₁₀,where R₁₀ is C₁ -C₁₂ alkyl or C₅ -C₁₂ cycloalkyl or C₇ -C₉ phenylalkylor phenyl; or R₇ and R₈, independently of each other, are C₆ -C₁₂ arylwhich is substituted by a residue selected from C₁ -C₄ alkyl, C₁ -C₄alkoxy, halogen; and both of R₂₀ and R₂₁ are either hydrogen or halogen;wherein a compound of the formula (II) as described in claim 1 isoxidized and the resulting intermediate of formula (I) is subjected tohydrogenation and/or halogenation.
 6. A process according to claim 1,wherein the compound of the formula (I) conforms to the formula (Ia)##STR82## in which the index n ranges from 1 to 15; R₁₂ is C₂ -C₁₂alkylene, C₄ -C₁₂ alkenylene, C₅ -C₇ cycloalkylene, C₅ -C₇cycloalkylenedi(C₁ -C₄ alkylene), C₁ -C₄ alkylenedi(C₁ -C₇cycloalkylene), phenylenedi(C₁ -C₄ alkylene) orC₄ -C₁₂ alkyleneinterrupted by 1,4-piperazinediyl, --O-- or >N--X₁ with X₁ being C₁ -C₁₂acyl or (C₁ -C₁₂ alkoxy)carbonyl or having one of the definitions of R₁₄given below except hydrogen; or R₁₂ is a group of the fornula (Ib') or(Ic'); ##STR83## X₂ being C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which isunsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkyl; phenyl which isunsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkyl or C₁ -C₄ alkoxy;C₇ -C₉ phenylalkyl which is unsubstituted or substituted on the phenylby 1, 2 or 3 C₁ -C₄ alkyl; and the radicals X₃ being independently ofone another C₂ -C₁₂ alkylene; the radicals A are independently of oneanother --OR₁₃, --N(R₁₄)R₁₅) or a group of the formula (Id'); ##STR84##R₁₃, R₁₄ and R₁₅, which are identical or different, are hydrogen, C₁-C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which is unsubstituted or substituted by1, 2 or 3 C₁ -C₄ alkyl; C₃ -C₁₈ alkenyl, phenyl which is unsubstitutedor substituted by 1, 2 or 3 C₁ -C₄ alkyl or C₁ -C₄ alkoxy; C₇ -C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2or 3 C₁ -C₄ alkyl; tetrahydrofurfuryl or C₂ -C₄ alkyl which issubstituted in the 2, 3 or 4 position by --OH, C₁ -C₈ alkoxy, di(C₁ -C₄alkyl)amino or a group of the formula (Ie'); ##STR85## with Y being--O--, --CH₂ --, --CH₂ CH₂ -- or >N--CH₃, or --N(R₁₄)(R₁₅) isadditionally a group of the formula (Ie'); X is --O-- or >N--R₁₆ ; R₁₆is hydrogen, C₁ -C₁₈ alkyl, C₃ -C18alkenyl, C₅ -C₁₂ cycloalkyl which isunsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkyl; C₇ -C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2or 3 C₁ -C₄ allyl; tetrahydrofuryl, a group of the formula (If'),##STR86## or C₂ -C₄ alkyl which is substituted in the 2, 3 or 4 positionby --OH, C₁ -C₈ alkoxy, di(C₁ -C₄ alkyl)amino or a group of the formula(Ie'); R₁₁ has one of the definitions given for R₁₆ ; and the radicals Bhave independently of one another one of the definitions given for A. 7.A process according to claim 5, wherein the compound of the formula (V)conforms to the formula (IIIb) ##STR87## in which the index n rangesfrom 1 to 15; R₁₂ is C₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, C₅ -C₇cycloalkylene, C₅ -C₇ cycloalkylenedi(C₁ -C₄ alkylene), C₁ -C₄alkylenedi(C₅ -C₇ cycloalkylene), phenylenedi(C₁ -C₄ alkylene) or C₄-C₁₂ alkylene interrupted by 1,4-piperazinediyl, --O-- or >N--X₁ with X₁being C₁ -C₁₂ acyl or (C₁ -C₁₂ alkoxy)carbonyl or having one of thedefinitions of R₁₄ given below except hydrogen; or R₁₂ is a group of theformula (Ib') or (Ic'); ##STR88## X₂ being C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄alkyl; phenyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄alkyl or C₁ -C₄ alkoxy; C₇ -C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁ -C₄ alkyl; andthe radicals X₃being independently of one another C₂ -C₁₂ alkylene; the radicals A areindependently of one another --OR₁₃, --N(R₁₄)(R₁₅) or a group of theformula (IIId); ##STR89## R₁₃, R₁₄ and R₁₅, which are identical ordifferent, are hydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which isunsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkyl; C₃ -C₁₈ alkenyl,phenyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄ alkylor C₁ -C₄ alkoxy; C₇ -C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁ -C₄ alkyl; tetrahydrofurfurylor C₂ -C₄ alkyl which is substituted in the 2, 3 or 4 position by --OH,C₁ -C₈ alkoxy, di(C₁ -C₄ alkyl)amino or a group of the formula (Ie');##STR90## with Y being --O--, --CH₂ --, --CH₂ CH₂ -- or >N--CH₃, or--N(R₁₄)(R₁₅) is additionally a group of the formula (Ie'); X is --O--or >N--R₁₆ ; R₁₆ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₈ alkenyl, C₅ -C₁₂cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C₁ -C₄alkyl; C₇ -C₉ phenylalkyl which is unsubstituted or substituted on thephenyl by 1, 2 or 3 C₁ -C₄ alkyl; tetrahydrofurfuryl, a group of theformula (IIIf), ##STR91## or C₂ -C₄ alkyl which is substituted in the 2,3 or 4 position by --OH, C₁ -C₈ alkoxy, di(C₁ -C₄ alkyl)amino or a groupof the formula (Ie'); R₁₁ has one of the definitions given for R₁₆ ; andthe radicals B have independently of one another one of the definitionsgiven for A.